Catalyst with lanthamide-doped zirconia and methods of making

ABSTRACT

The invention generally relates to three-way catalysts and catalyst formulations capable of simultaneously converting nitrogen oxides, carbon monoxide, and hydrocarbons into less toxic compounds. Such three-way catalyst formulations contain ZrO 2 -based mixed-metal oxide support oxides doped with an amount of lanthanide. Three-way catalyst formulations with the support oxides of the present invention demonstrate higher catalytic activity, efficiency and longevity than comparable catalysts formulated with traditional support oxides.

CROSS REFERENCE TO RELATED APPLICATION

This application claims priority to U.S. Provisional Application No.61/521,831, filed Aug. 10, 2011, which is incorporated herein byreference in its entirety.

TECHNICAL FIELD OF INVENTION

The invention generally relates to three-way catalysts and catalystformulations capable of simultaneously converting nitrogen oxides,carbon monoxide, and hydrocarbons into less toxic compounds. Suchthree-way catalyst formulations contain ZrO₂-based mixed-metal oxidesupport oxides doped with an amount of lanthanide. Three-way catalystformulations with the support oxides of the present inventiondemonstrate higher catalytic activity, efficiency and longevity thancomparable catalysts formulated with traditional support oxides.

BACKGROUND OF THE INVENTION

Nitrogen oxides, carbon monoxide, and hydrocarbons are toxic andenvironmentally damaging byproducts found in the exhaust gas frominternal combustion engines. Methods of catalytically convertingnitrogen oxides, carbon monoxide, and hydrocarbons into less harmfulcompounds include the simultaneous conversion of these byproducts (i.e.,“three-way conversion” or “TWC”). Specifically, nitrogen oxides areconverted to nitrogen and oxygen, carbon monoxide is converted to carbondioxide, and hydrocarbons are converted to carbon dioxide and water.

It has generally been found that TWC increases catalytic activity andefficiency and, thus, aids in meeting emission standards for automobilesand other vehicles. In order to achieve an efficient three-wayconversion of the toxic components in the exhaust gas, conventional TWCcatalysts contain large quantities of precious metals, such as Pd, Ptand Rh, dispersed on suitable oxide carriers. Typically, conventionalTWC catalysts use precious metal catalysts at concentrations in therange of 30-300 g/ft³, with Rh, being used in the range of 5-30 g/ft³.

Commonly used catalyst systems suffer from several drawbacks. Forexample, commonly used TWC catalyst systems require precious metalcatalysts in order to efficiently carry out the TWC. Such preciousmetals are expensive, can be inefficient, and have been shown to degradeover time/use.

There have been several previous attempts at improving the light-offperformance of catalyst systems. Such attempts have tried to addressproblems relating to inefficiency of precious metal catalysts at lowertemperatures and the degradation of such catalysts as a result ofexposure to high temperatures. For example, some approaches utilizehigher loadings of active precious metal catalysts (e.g., Rh) withpredictable increases in cost. Other approaches have utilized substratestructures with a higher channel density (and, thus, higher amounts ofprecious metal catalyst). These approaches not only suffer fromincreases in cost, but also from higher back pressure. The higher backpressure, which is an artifact of the fact that the higher channeldensity decreases the amount of space through which exhaust may pass,results in an increase in fuel usage. A third approach has been to use adual TWC system. Such TWC systems comprise a first TWC catalyst placednear the engine (i.e., a close coupled “CC” catalyst), thus exposing itto the engine's heat exhaust and allowing it to reach light-offtemperature more quickly and a second, larger, TWC catalyst placedfurther away from the engine (e.g., under the floor of the vehicle)where there additional space allows for the placement of larger TWCcatalysts systems. While such techniques lead to improved TWC catalystefficiencies, they tend to decrease the lifespan of at least the CC TWCcatalyst by exposing it to higher temperatures. In addition, CC TWCcatalysts suffer from increased poisoning of the precious metalcatalysts by virtue of their increased exposure to sulfur or phosphorousin engine exhaust. Thus, there is a trade-off between increasingcatalyst efficiency at the expense of decreasing lifespan and, thus,requiring the expensive replacement of TWC catalysts.

Other methods for improving light-off performance focused on modifyingthe layout of the PGM catalysts in CC TWC catalysts. For example, somemethods place additional or extra PGM catalysts at the front of the CCTWC catalysts as a further means of quickly bringing catalysts to theirlight-off temperatures. As can be expected, such catalyst designs sufferfrom the same drawbacks discussed above—decreased lifespan by thermaldegradation of the catalyst and poisoning of the catalysts by virtue ofthe fact that they are exposed to higher amounts of upstream exhaust—inaddition to the fact that they require increased amounts of expensivePGM catalysts.

Thus, there is a need for catalyst formulations which have increasedconversion efficiencies without requiring additional amounts of preciousmetals.

SUMMARY OF THE INVENTION

In some embodiments, the present invention relates to a support oxidecomprising ZrO₂ doped with an amount of lanthanide. In additionalembodiments, the support oxide further comprises Al₂O₃ or La—Al₂O₃. Insome embodiments, the lanthanide used is La or Pr. Such support oxidesare generally referred to herein as La—ZrO₂-based mixed-metal oxidesupport oxides (MMOSOs). The amount of lanthanide present in the supportoxide can vary. For example, the ZrO₂ support oxide may be doped withbetween about 1-30% of the lanthanide. In some embodiments, the ZrO₂support oxide is doped with between about 5-15% of the lanthanide. Inother embodiments, the ZrO₂ support oxide is doped with about 5%, 10% or15% of the lanthanide.

In particular embodiments, the support oxide comprisesLa_(X %)Zr_((1-X) %)O₂ and/or Pr_(X %)Zr_((1-X) %)O₂. In otherparticular embodiments, the support oxide comprises La_(5%)Zr_(95%)O₂,Pr_(5%)Zr_(95%)O₂, La_(10%)Zr_(90%)O₂, Pr_(10%)Zr_(90%)O₂,La_(15%)Zr_(85%)O₂, Pr_(15%)Zr_(85%)O₂, or mixtures thereof.

The support oxides of the present invention are stabilized in thetetragonal phase. Accordingly, the present invention refers to supportoxides wherein the tetragonal phase is stabilized.

In some embodiments, the support oxides further comprise an oxygenstorage material (OSM). Suitable OSMs include those of the generalformula Ce_(1-a-b-c-d)D_(a)E_(b)F_(c)Zr_(d)O₂, wherein a, b and c are,independently, 0-0.7; d is 0-0.9; and D, E and F are, independently,selected from the group consisting of lanthanides, alkaline earth metalsand transition metals. In a particular embodiment, the OSM isCe_(0.3)Nd_(0.05)Pr_(0.05) Zr_(0.6)O₂.

In another aspect, the present invention relates to washcoats comprisingLa—ZrO₂-based MMOSOs, an OSM and a catalyst. In some embodiments, thecatalyst is a platinum group metal (PGM) catalyst. Examples of suitablePGM catalysts include Rh, Pt, Pd, or mixtures thereof. In particularembodiments, the PGM is Rh. In additional particular embodiments, the Rhis present at 0.25% (by weight) of the washcoat.

The present invention similarly relates to overcoats comprisingLa—ZrO₂-based MMOSOs, an OSM and a catalyst. In some embodiments, thecatalyst is a platinum group metal (PGM) catalyst. Examples of suitablePGM catalysts include Rh, Pt, Pd, or mixtures thereof. In particularembodiments, the PGM is Rh. In additional particular embodiments, the Rhis present at 0.25% (by weight) of the overcoat.

The washcoats and overcoats of the present invention may constitutevarying amounts of the La—ZrO₂-based MMOSOs. For example, theLa—ZrO₂-based MMOSO may constitute 1-100% (by weight) of the washcoat orovercoat. In some embodiments, the La—ZrO₂-based MMOSO constitutes40-80%, 45-75%, 50-70% or 55-65% (by weight) of the washcoat orovercoat. In other embodiments, the La—ZrO₂-based MMOSO constitutes 60%(by weight) of the washcoat or overcoat.

Moreover, the washcoats and overcoats of the present invention mayconstitute varying amounts of OSMs. For example, in some embodiments,the OSM constitutes 30-50% (by weight) of the washcoat or overcoat. Inother embodiments, the OSM constitutes 40% (by weight) of the washcoator overcoat.

In particular embodiments, the washcoat or overcoat comprises about:

a) (i) 40% oxygen storage material (OSM); (ii) 30% Al₂O₃ or La—Al₂O₃;and (iii) 30% Pr_(0.05)Zr_(0.95)O₂;

b) (i) 40% OSM; (ii) 30% Al₂O₃ or La—Al₂O₃; and (iii) 30%La_(0.05)Zr_(0.95)O₂;

c) (i) 40% OSM; 30% Al₂O₃ or La—Al₂O₃; and (iii) 30%Pr_(0.10)Zr_(0.90)O₂;

d) (i) 40% OSM; 30% Al₂O₃ or La—Al₂O₃; and (iii) 30%La_(0.10)Zr_(0.90)O₂;

e) (i) 40% OSM; 30% Al₂O₃ or La—Al₂O₃; and (iii) 30%Pr_(0.15)Zr_(0.85)O₂;

f) (i) 40% OSM; 30% Al₂O₃ or La—Al₂O₃; and (iii) 30%La_(0.15)Zr_(0.85)O₂;

g) (i) 40% OSM; and (ii) 60% Pr_(0.05)Zr_(0.95)O₂;

h) (i) 40% OSM; and (ii) 60% La_(0.05)Zr_(0.95)O₂;

i) (i) 40% OSM; and (ii) 60% Pr_(0.10)Zr_(0.90)O₂;

j) (i) 40% OSM; and (ii) 60% La_(0.10)Zr_(0.90)O₂;

k) (i) 40% OSM; and (ii) 60% Pr_(0.15)Zr_(0.85)O₂; or

l) (i) 40% OSM; and (ii) 60% La_(0.15)Zr_(0.85)O₂.

In another aspect, the present invention relates to catalyst systemscomprising a substrate and a washcoat, wherein the washcoat comprises aLa—ZrO₂-based MMOSO, as described above. In addition, the presentinvention relates to catalyst systems comprising a substrate, awashcoat, and an overcoat, wherein the washcoat comprises aLa—ZrO₂-based MMOSO, as described above, and the overcoat comprises asupport oxide, OSM, and a catalyst. In such embodiments, the catalyst inthe overcoat may be Rh, Pt, Pd, or a mixture thereof, preferably Pd. Inspecific embodiments, the catalyst in the overcoat is Pd and is presentat 100 g/ft³.

The present invention further relates to catalyst systems comprising asubstrate, a washcoat, and an overcoat, wherein the washcoat comprises asupport oxide, an OSM and a catalyst, and the overcoat comprises aLa—ZrO₂-based MMOSO, as described above. In such embodiments, thecatalyst in the washcoat may be Rh, Pt, Pd, or a mixture thereof,preferably Pd. In specific embodiments, the catalyst in the washcoat isPd and is present at 100 g/ft³.

The catalyst systems of the present invention may be TWC catalystsystems. In addition, the catalyst systems may improve gas flow and/orlight-off performance when compared to catalyst systems comprising onlytraditional support oxides.

The present invention also relates to methods of making the catalystsystems described above. For example, the present invention relates to amethod of making a catalyst system comprising: a) depositing a washcoatcomprising a La—ZrO₂-based MMOSO described above on a substrate; b)treating the washcoat and substrate by calcination; and c) optionallyimpregnating a PGM catalyst into the washcoat, followed by drying andcalcination.

The present invention also relates to a method of making a catalystsystem comprising: a) depositing a washcoat comprising a La—ZrO₂-basedMMOSO described above on a substrate; b) treating the washcoat andsubstrate by calcination; c) optionally impregnating a PGM catalyst intothe washcoat, followed by drying and calcination; d) depositing anovercoat onto the washcoat, wherein the overcoat comprises a supportoxide, an OSM and a catalyst; and e) optionally impregnating a PGMcatalyst into the overcoat, followed by drying and calcination.

In addition, the present invention relates to a method of making acatalyst system comprising: a) depositing a washcoat on a substrate,wherein the washcoat comprises a support oxide, an OSM and a catalyst;b) treating the washcoat and substrate by calcination; c) optionallyimpregnating a PGM catalyst into the washcoat, followed by drying andcalcination; d) depositing an overcoat comprising La—ZrO₂-based MMOSOdescribed above onto the washcoat; and e) optionally impregnating a PGMcatalyst into the overcoat, followed by drying and calcination.

In each of the above methods, the washcoat (and overcoat, whereapplicable) may be deposited as a slurry. In such embodiments, the PGMcatalyst may be preloaded onto the slurry. Such preloaded PGM catalystsmay be in the form of a nitrate, acetate or chloride salt.

In embodiments wherein the PGM catalyst is impregnated onto a washcoat(or overcoat, where applicable) the PGM catalyst may be impregnated asan aqueous solution. PGM catalysts may be in the form of a nitrate,acetate or chloride salt.

The present invention also relates to methods of reducing toxic exhaustgas emissions comprising contacting gas emissions with the catalystsystems described above. In addition, the present invention refers tomethods of increasing oxygen flow through a catalytic system bystabilizing the phase (in, for example, the tetragonal phase) of thesupport oxide present in the catalyst system. In some embodiments, thecatalyst system used in these methods comprises a La—ZrO₂-based MMOSOdescribed above. In other embodiments, the catalyst system used in thesemethods is a catalyst system described above.

In addition, the present invention relates to methods of improving thelifetime of a catalyst system comprising a PGM catalyst by: a) reducingthe amount of PGM catalyst deactivated during the aging of the catalystsystem; b) increasing the amount of metallic PGM initially present inthe catalyst system; or c) both a) and b). In some embodiments, thecatalyst system used in these methods comprises a La—ZrO₂-based MMOSOdescribed above. In other embodiments, the catalyst system used in thesemethods is a catalyst system described above. In some embodiments theamount of Rh(0) and/or Rh(III) as Rh₂O₃ initially present in thecatalyst system is increased. In other embodiments, the amount of Rh(0)which is converted to Rh(III) as Rh₂O₃ or Rh(III)-MMO during aging ofthe catalyst system is decreased. In a particular embodiment, the amountof Rh(0) which is converted to Rh(III)-MMO during aging of the catalystsystem is decreased.

The present invention further relates to methods of improving theconversion of a) nitrogen oxides to nitrogen and oxygen; b) hydrocarbonsto carbon dioxide and water; or c) both a) and b), present in exhaustgas emissions, by utilizing La—ZrO₂-based MMOSOs described above in thewashcoat, optional overcoat, or both. The present invention also relatesto methods of improving the light-off performance of a catalyst systemby utilizing La—ZrO₂-based MMOSOs described above in the washcoat,optional overcoat, or both. Moreover, the present invention relates tomethods of reducing the amount of PGM present in a catalyst system whilemaintaining catalyst efficiency by utilizing La—ZrO₂-based MMOSOsdescribed above in the washcoat, optional overcoat, or both. Inparticular embodiments of each of these methods, the PGM is Rh.

Methods of TWC of gas emissions comprising contacting gas emissions withthe catalyst systems described above are also contemplated by thepresent invention.

In some embodiments, the present invention relates to catalyticconvertor systems comprising the catalyst system described above. Suchcatalytic convertor systems may comprise two or more catalyticconverters. In some embodiments, the catalytic convertor systemcomprises a close coupled catalytic converter.

BRIEF DESCRIPTION OF THE FIGURES

FIG. 1 is a schematic representation of a TWC catalyst comprising (1) asubstrate, and (2) a washcoat containing at least one metal catalyst,wherein the washcoat is supported by the substrate.

FIG. 2 is a schematic representation of a TWC catalyst comprising (1) asubstrate, (2) a washcoat containing at least one metal catalyst,wherein the washcoat is supported by the substrate, and (3) an overcoatcontaining at least one metal catalyst, wherein the overcoat issupported by the washcoat.

FIG. 3 is a schematic representation of a TWC catalyst comprising (1) asubstrate, (2) a washcoat containing at least one metal catalyst,wherein the washcoat is supported by the substrate, and (3) an overcoatwhich is free of metal catalyst.

FIG. 4 is a schematic representation of a TWC catalyst comprising (1) asubstrate, (2) a washcoat which is free of metal catalyst and (3) anovercoat containing at least one metal catalyst, wherein the overcoat issupported by the washcoat.

FIG. 5 shows an X-ray powder diffraction plot illustrating the relativeamounts of tetragonal vs monoclinic phase in ZrO₂-based MMOSO doped with5%, 10% or 15% Pr. The tested MMOSO had not been aged. It is noted thatthe tetragonal phase is the only phase detected in MMOSOs doped with 10%and 15% Pr.

FIG. 6 Shows an X-ray powder diffraction plot illustrating the relativeamounts of tetragonal vs monoclinic phase in ZrO₂-based MMOSO doped with5%, 10% or 15% Pr after aging at 1000° C. for 20 hours. The dataindicates that increasing the Pr content increases the stability of thetetragonal phase to aging.

FIG. 7 is a diagram illustrating the steric hindrance presented by Pr³⁺cations. Oxygen mobility occurs via a “hopping” mechanism. That is, theoxygen anion “hops” to a neighboring vacant site which is usuallypresent due to lattice defects or the fact that two Pr³⁺ atoms areadjacent to each other. The presence of too many Pr³⁺ cations makes itdifficult for relatively large oxygen anion to migrate through thelattice.

FIG. 8 is a diagram illustrating that the inter-domain boundary betweenmonoclinic and tetragonal facilitates gas diffusion and plays a role asa gas diffusion pathway. Thus, stabilization of the tetragonal phase byPr doping leads to faster and easier diffusion of oxygen through thecatalyst structure.

FIG. 9 is a plot of lattice parameter versus Pr content of the MMOSO.The data indicate a linear relationship between the amount of Printroduced into the support oxide and the lattice parameters. The factthat Pr affects the lattice parameters in this respect signifies that asolid solution exists between Pr and Zr rather separate phases.

FIG. 10 is a plot of the rate of H₂ absorption and of cumulativehydrogen absorption vs temperature for the 550° C. TPO-TPR cycle. As theamount of Pr increased, the major Rh and Rh-MMO reduction peaks (A+B)shifted to lower temperatures, indicating lower light-off temperatures.It is noted that the 5% Pr and 10% Pr loaded samples had the highesttotal H₂ absorption.

FIG. 11 is a plot of the rate of H₂ absorption vs temperature for the900° C. TPO-TPR cycle. The 10% Pr loaded sample exhibited the highesttotal H₂ absorption.

FIG. 12 is a plot of cumulative H₂ absorption vs temperature for the900° C. TPO-TPR cycle. The 10% Pr loaded sample exhibited the highesttotal H₂ absorption.

FIG. 13 is a plot of the rate of H₂ absorption vs temperature for the1000° C. XHFC aging. At 25° C., H₂ absorption can be ranked as follows:(15% Pr)=(10% Pr)>(5% Pr)>(0% Pr). The 10% Pr loaded sample had thehighest total H₂ absorption.

FIG. 14 is a plot of the rate of H₂ absorption and of cumulativehydrogen absorption versus temperature for the 1000° C. XHFC aging. At25° C., H₂ absorption can be ranked as follows: (15% Pr)=(10% Pr)>(5%Pr)>(0% Pr). The 10% Pr loaded sample had the highest total H₂absorption.

FIG. 15 is a flowchart illustrating the generation of an overcoatcontaining a Pr—ZrO₂-based MMOSO.

FIG. 16 is a flowchart illustrating the steps of the IWCP.

DETAILED DESCRIPTION OF THE INVENTION

In order that the invention herein described may be fully understood,the following detailed description is set forth.

Unless defined otherwise, all technical and scientific terms used hereinhave the same meaning as those commonly understood by one of ordinaryskill in the art to which this invention belongs. Although methods andmaterials similar or equivalent to those described herein can be used inthe practice or testing of the present invention, suitable methods andmaterials are described below. The materials, methods and examples areillustrative only, and are not intended to be limiting. Allpublications, patents and other documents mentioned herein areincorporated by reference in their entirety.

Throughout this specification, the word “comprise” or variations such as“comprises” or “comprising” will be understood to imply the inclusion ofa stated integer or groups of integers but not the exclusion of anyother integer or group of integers.

In order to further define the invention, the following terms anddefinitions are provided herein.

DEFINITIONS

The term “catalyst system” refers to any system comprising a catalystsuch as a PGM catalyst. In some embodiments, the catalyst systemcomprises a substrate, a washcoat, and optionally an overcoat. Examplesof catalyst systems are depicted in FIGS. 1-4.

The term “close-coupled catalyst” or “CC catalyst” refers to, forexample, a catalytic converter which is placed close to the engine so asto be exposed to the heat generated by operation of the engine. Such CCcatalysts may be TWC catalysts.

The term “Ce-containing mixed metal oxide” refers to materials based ona fluorite structure and containing Ce, Zr and, typically, severallanthanide metals. Typical examples are expressed in terms of therelative quantity of Ce and Zr (Ce-rich or Zr-rich) and the nature ofthe lanthanide dopants at the 1-10% level typically.

The term “conversion efficiency” refers to the percentage of emissionspassing through the catalyst that are converted to their targetcompounds.

The term “coupled with” refers to a relationship (e.g., functional orstructural) between components of a catalyst system (e.g., therelationship between the washcoat and the substrate and/or overcoat, orthe relationship between the overcoat and the washcoat). In someembodiments, components which are coupled to each other are in directcontact with each other (e.g., the washcoat may be in direct contactwith and, thus, coupled with the substrate). In other cases, componentswhich are coupled to each other are coupled via additional component(s)(e.g., an overcoat is coupled to the substrate via the washcoat).

The term “high-surface area alumina” refers to aluminum oxides that havea high specific surface area—i.e., a high surface area per unit weight.High surface area aluminas typically have crystal structures designatedas gamma, delta or theta.

The term “high-temperature conditions” refers to engine conditionswherein hot exhaust gas passes through a catalyst. Such exhaust gas istypically in excess of 800° C., and in extreme circumstances, in excessof 1000° C.

The term “Lanthanide group of elements” refers to the elements La, Pr,Sm, Nd, Pm, Gd, Eu, Tb, Dy, Ho, Er, Tm, Yb and Lu.

The term “Ln-doped Zirconia” refers to an oxide comprising zirconium andan amount of dopant from the Lanthanide group of elements, where Lndenotes any of the lanthanide group.

The term “light-off temperature” refers to the temperature at which acatalyst is able to convert 50% of the emissions passing through thecatalyst (e.g., nitrogen oxides, carbon monoxide and unburnthydrocarbons) to their target compounds (e.g., nitrogen and oxygen,carbon dioxide, and carbon dioxide and water, respectively).

The term “metallic Rh” refers to the element Rh in its metallic state“Rh(0).” The term “Rh(I)” refers to mono-valent Rhodium (metallic Rhwith one electron removed). The term “Rh(III)” refers to tri-valentRhodium (metallic Rh with three electrons removed). Rh(III) is thestable form of Rh found in, e.g., Rh₂O₃.

The term “mixed metal oxide” refers to an oxide, wherein the cationpositions in the oxide's crystal structure can be occupied by a varietyof cations. Such cations may be selected from one or a variety oflanthanides. In particular embodiments, the mixed metal oxide cationsare a mixture of either Pr and Zr, or La and Zr. The term “multiphasecatalyst” or “MPC” refers to a catalyst represented by the generalformula CeyLn1-xAx+sMOz. Such catalysts are described in, e.g., U.S.Pat. No. 7,641,875, which is incorporated herein in its entirety.

The term “overcoat” refers to a coating comprising one or more oxidesolids that are coupled with a substrate and a washcoat. The oxidesolids in the overcoat may be support oxides, one or more catalystoxides, or a mixture of support oxides and catalyst oxides.

The term “oxygen storage material” or “OSM” refers to a compositionwhich supplies oxygen to rich exhaust and takes up oxygen from leanexhaust, thus buffering a catalyst system against the fluctuating supplyof oxygen. OSMs increase catalyst efficiency. Oxygen storage materialsmay be present in the washcoat and/or the overcoat of a catalyst system.

The term “platinum group metal” or “PGM” refers to the following sixelements: ruthenium (Ru), rhodium (Rh), palladium (Pd), osmium (Os),iridium (Ir), and platinum (Pt).

The term “poisoning” or “catalyst poisoning” refers to the inactivationof a catalyst by virtue of its exposure to lead or phosphorous in, forexample, engine exhaust.

The term “solid solution” refers to the doping of a metal either ontothe crystallographic site of a host material, or in betweencrystallographic sites of a host material. Such solid solutions arecomposed of a single homogenous phase. The solid solution has the samecrystallographic type or structure as the un-doped host material.Typically the lattice parameters of the solid solution increase ordecrease with increasing dopant amount. Whether or not an increase ordecrease in lattice parameters occurs depends on whether the dopingcation is smaller or larger than the host cations (in addition to otherspecific chemical and crystallographic factors).

The term “stoichiometric point” or “stoichiometric ratio” refers to aparticular air-fuel ratio (i.e., the ratio of air to fuel present in anengine during combustion). An engine operates at the stoichiometricpoint when exactly enough air is present in the fuel mixture to burn allof the fuel present.

The term “stabilized alumina” refers to alumina wherein modifiers areadded to retard undesired phase transitions of the alumina from, forexample, the gamma phase to the alpha phase, when the alumina is exposedto elevated temperatures. Such modifiers aid in stabilizing the surfacearea of the alumina. Alumina is exposed to high temperatures duringformation of the catalyst system and during operation of the catalystsystem (e.g., when it is exposed to exhaust gas). The modifiers orthermal stabilizers may include, for example, one or more modifiers orstabilizers selected from, but not limited to, rare earth oxides,silicon oxides, oxides of Group IVB metals (e.g., zirconium, hafnium, ortitanium) and alkaline earth oxides. For example, lanthanide nitrateand/or strontium nitrate may be added to washcoats and/or overcoats (in,e.g., support oxides) as a modifier for the alumina. The lanthanidenitrate solution may contain a single lanthanide nitrate (e.g.,lanthanum nitrate), or the solution may contain a mixture of lanthanidenitrates. Heating or calcining the lanthanide nitrate and/or strontiumnitrate forms lanthanide oxide (Ln₂O₃) and/or strontium oxide.

The term “substrate” refers to any material known in the art forsupporting a catalyst. Substrates can be of any shape or configurationthat yields a sufficient surface area for the deposit of the washcoatand/or overcoat. Examples of suitable configurations for substratesinclude, but are not limited to, honeycomb, pellet, and beadconfigurations. Substrates can be made of a variety of materialsincluding, but not limited to alumina, cordierite, ceramic and metal.

The term “three-way conversion catalyst” or “TWC catalyst” refers to acatalyst that simultaneously a) reduces nitrogen oxides to nitrogen andoxygen; b) oxidizes carbon monoxide to carbon dioxide; and c) oxidizesunburnt hydrocarbons to carbon dioxide and water. Typically, TWCcatalysts require the use of precious metals such as platinum groupmetals.

The term “washcoat” refers to a coating comprising one or more oxidesolids that is coupled to a substrate or solid support structure. Theoxide solids in the washcoat may be support oxides, one or more catalystoxides, or a mixture of support oxides and catalyst oxides.

Catalyst Systems

Catalyst systems in, for example, catalytic converters may be used inconjunction with an internal combustion engine. Such catalyst systemsmay be TWC catalysts. In light of the expense associated withRh-containing catalyst systems, there remains a need for catalystsystems with improved Rh efficiencies and Rh longevity. Thus, in oneaspect, the present invention provides catalyst system components whichimprove Rh efficiencies and Rh longevity.

The catalyst systems (including TWC catalyst systems) of the presentinvention may have a variety of architectures. TWC catalyst systemstypically comprise (1) a substrate, (2) a washcoat supported by thesubstrate, and (3) an optional overcoat supported by the washcoat (see,FIGS. 1-4). For example, the TWC catalyst systems of the presentinvention may comprise (1) a substrate, and (2) a washcoat containing atleast one catalyst, wherein the washcoat is supported by the substrate(see, FIG. 1). The catalyst systems of the present invention may alsocomprise (1) a substrate, (2) a washcoat containing at least onecatalyst, wherein the washcoat is supported by the substrate, and (3) anovercoat containing at least one catalyst, wherein the overcoat issupported by the washcoat (see, FIG. 2). The catalyst systems of thepresent invention may also comprise (1) a substrate, (2) a washcoatcontaining at least one catalyst, wherein the washcoat is supported bythe substrate, and (3) an overcoat which is relatively free of catalyst,preferably at least 95%, 99%, or at least 99.99% free of catalystcompletely free (see, FIG. 3). Further, the catalyst systems of thepresent invention may comprise (1) a substrate, (2) a washcoat which isrelatively free of catalyst, preferably at least 95%, 99%, or at least99.99% free of catalyst, and (3) an overcoat containing at least onecatalyst, wherein the overcoat is supported by the washcoat (see, FIG.4).

Catalyst systems are typically present in two locations in automobileengines. For example, an automobile may contain two catalyticconverters: 1) a close-coupled catalyst (“CC catalyst”) placed near theengine; and 2) a larger catalyst placed, for example, under the floor ofthe vehicle where there is more room (“underfloor catalyst” of “UFcatalyst”). CC catalysts are placed near the engine so they are exposedto the heat generated by operation of the engine. This heat allows theCC catalyst to more quickly reach its light-off temperature and, thus,more quickly reach its maximum efficiency. The catalyst systems of thepresent invention may be used in either CC or UF catalysts. In someembodiments, the catalysts systems of the present invention improve thelifetime and efficiency of CC catalysts containing Rh, even in light ofthe exposure of CC catalysts to elevated engine exhaust temperatures.

Improved Catalyst Systems

One aspect of the present invention is the provision of catalyst systemcomponents with improved Rh efficiencies and Rh longevity. Suchcomponents may be used in the washcoat and/or overcoats of catalystsystems. Specifically, the present invention provides support oxides forusing in washcoats and/or overcoats which improve Rh efficiencies and Rhlongevity. In particular embodiments, the support oxides are comprisedof alumina doped with an amount of lanthanide such as praseodymium (Pr)or Lanthanum (La).

Lanthanide Doped Support Oxides

The mixed-metal oxide support oxides (MMOSOs) of the present inventionimprove the catalyst properties of, for example, TWC catalysts asdescribed herein. Specifically, the MMOSOs of the present inventiondemonstrate higher catalytic activity, efficiency and longevity thancomparable catalysts formulated with traditional support oxides. Forexample, the MMOSOs of the present invention improve the light-offtemperature, stability/lifetime of the precious metal catalysts such asRh, and oxygen flow in catalyst systems. In particular embodiments, theMMOSOs of the present invention improve the light-off temperature andstability/lifetime of Rh catalysts present in TWC catalyst systems.

In one aspect, the present invention refers to improved support oxidesfor use in catalyst systems. The support oxides of the present inventionare MMOSOs such as, for example, ZrO₂-based MMOSOs. It has been foundthat doping ZrO₂-based MMOSOs with an amount of lanthanide yieldssupport oxides with the improved properties discussed herein. Inparticular, the support oxides of the present invention have been dopedwith an amount of lanthanide to yield Ln-ZrO₂-based MMOSOs. In general,the doped ZrO₂-based MMOSOs of the catalyst systems are of the followingformula:

Ln_(X %)Zr_((1-X) %)O₂,

-   -   wherein “X”=the amount (% by weight) of Ln cation present in the        catalyst; and    -   “1−X”=the amount by weight of Zr cation present in the catalyst.

Any lanthanide (e.g., La, Pr, Sm, Nd, Pm, Gd, Eu, Tb, Dy, Ho, Er, Tm, Ybor Lu) may be used in the MMOSOs of the present invention. In aparticular embodiment, the lanthanide used is either La or Pr. In someembodiments, the catalyst systems comprise a La—ZrO₂-based MMOSO, aPr—ZrO₂-based MMOSO, or both. Thus, in one embodiment, the catalystsystems comprise an amount, as described herein, ofPr_(X %)Zr_((1-X) %)O₂. In another embodiment, the catalyst systemscomprise an amount, as described herein, of La_(X %)Zr_((1-X) %)O₂. Inyet another embodiment, the catalyst systems comprise an amount, asdescribed herein, of Pr_(X %)Zr_((1-X) %)O₂ and La_(X %)Zr_((1-X) %)O₂.

The ZrO₂-based MMOSO can be doped with varying amounts of a lanthanide,such as La or Pr, to yield a Ln-ZrO₂-based MMOSO. For example, theZrO₂-MMOSO may be doped with about 1%, 2%, 3%, 4%, 5%, 6%, 7%, 8%, 9%,10%, 11%, 12%, 13%, 14%, 15%, 16%, 17%, 18%, 19%, 20%, 21%, 22%, 23%,24%, 25%, 26%, 27%, 28%, 29% or 30% of a lanthanide. In someembodiments, the ZrO₂-MMOSO is doped with about 5%, 10%, 15%, 20%, 25%or 30% of a lanthanide. In other embodiments, the ZrO₂-MMOSO is dopedwith about 1-5%, 1-10%, 1-15%, 1-20%, 1-25%, 1-30%, 5-10%, 5-15%, 5-20%,or 10-15% of a lanthanide.

The ZrO₂-based MMOSO can also be doped with up to about 1%, 2%, 3%, 4%,5%, 6%, 7%, 8%, 9%, 10%, 11%, 12%, 13%, 14%, 15%, 16%, 17%, 18%, 19%,20%, 21%, 22%, 23%, 24%, 25%, 26%, 27%, 28%, 29% or 30% of a lanthanide,such as La or Pr, to yield a Ln-ZrO₂-based MMOSO. In some embodiments,the ZrO₂-based MMOSO is doped with up to about 5%, 10%, 15%, 20%, 25% or30% of a lanthanide. In other embodiments, the ZrO₂-based MMOSO is dopedwith up to about 1-5%, 1-10%, 1-15%, 1-20%, 1-25%, 1-30%, 5-10%, 5-15%,5-20%, or 10-15% of a lanthanide.

In particular embodiments, the ZrO₂-based MMOSO is doped with about 5%,10% or 15% a lanthanide, such as La or Pr, to yield a Ln-ZrO₂-basedMMOSO. In other embodiments, the ZrO₂-based MMOSO is doped with 5%, 10%or 15% a lanthanide, such as La or Pr. In one particular embodiment, theZrO₂-based MMOSO is doped with 10% of a lanthanide. For example, theLn-ZrO₂-based MMOSO may be: Pr_(5%)Zr_(95%)O₂; Pr_(10%)Zr_(90%)O₂;Pr_(15%)Zr_(85%)O₂; La_(5%)Zr_(95%)O₂; La_(10%)Zr_(90%)O₂; orLa_(15%)Zr_(85%)O₂.

Improved Catalyst Stability/Lifetime

Traditional catalyst systems typically utilize a high surface area“transition” alumina (as a support oxide) and a Ce-containing mixedmetal oxide (as an OSM). The high surface area alumina enables extensivedispersal of metal catalysts, such as Rh, allowing for effective accessof the exhaust to the catalyst sites. However, traditional catalystsystems suffer from drawbacks stemming from the interaction of the Rhcatalyst with the alumina support oxide under the high-temperatureconditions commonly found in modern automobile engines.

The reaction of Rh catalysts with other components in the catalystsystem (e.g., the support oxide) can negatively impact the efficiency ofRh-catalyzed reactions in a variety of conditions including, forexample, high temperature and high engine exhaust flow rate. The speciesof Rh most active for NO_(x) conversion to nitrogen gas is the metallicor Rh(0) state. During exposure of catalyst systems to high temperatureexhaust, however, the Rh(0) state is oxidized to a stable, and lessactive, Rh(III) state (i.e., Rh₂O₃). The less active Rh(III) state inthe Rh₂O₃ state can be converted back to Rh(0) via the oxidation cycleemployed during use of the catalyst. That is, Rh(III) present in theRh₂O₃ state may be reduced to Rh(0) through a reversible redox cycle.However, the presence of the less active Rh(III) state reduces theefficiency of the catalyst system.

In some instances, Rh(0) reacts with the alumina or ceria to form amixed oxide with Rh(III), resulting in a very stable and inactiveRh(III) mixed metal oxide state (Rh(III)-MMO). Rh(III)-MMO cannot bereduced to Rh(0) through a reversible redox cycle. Thus, Rh present inthe Rh(III)-MMO state and is essentially passivated or removed from thecatalytic cycle. Such conversions are described in, for example, in YaoH. C., Jaspar, S and Shelef. M, J. Catal., 50, p 407 (1977) and Yao H.C. and Gandhi H. S., J. Catal., 61, p 547 (1980), each of which isincorporated herein by reference in its entirety.

Rh(0) can also be negatively affected when it interacts with theCe-containing mixed metal oxide (the OSM). For example, during exposureto engine exhaust, Rh(0) is coated to or associated with theCe-containing mixed metal oxide. Thus, even though the Ce-containingmixed metal oxides are beneficial because they stabilize the tetragonalphase (discussed herein), their tendency to oxidize Rh(0) detracts fromtheir usefulness.

The overall effect of conversion of Rh(0) to either the Rh₂O₃ orRh(III)-MMO state is a decrease in the amount of active Rh(0) availableto act as a catalyst. The decrease in active Rh(0) is exacerbated by thefact that the efficiency of Rh-mediated catalysis is typically lower athigh temperatures (e.g. at or above 800° C.), which are typical ofhigh-speed engine conditions. For these reasons, traditional catalystsystems lead to an eventual reduction in the ability of Rh(0) to aid inNO_(x) conversion to nitrogen gas.

The present invention addresses the Rh conversion problem by reducingthe aging or degradation of the Rh in the TWC or TWC system caused byhigh-temperature conditions. This is accomplished by using the supportoxides (Ln-ZrO₂-based MMOSOs) described herein. The support oxides ofthe present invention allow the Rh to stay more predominantly in theRh(0) state.

Without being bound by a particular theory, it is believed that theLn-ZrO₂-based MMOSOs of the present invention reduce oxidation of Rh(0)for several reasons. First, the Ln-ZrO₂-based MMOSOs have propertieswhich allow them to store oxygen from exhaust gas and, in effect,sequester it from the Rh(0) catalyst. This reduces the opportunity forunwanted oxidation of Rh(0) to less desired Rh(III) states.

In addition, the Zr present in traditional support oxides has a tendencyto coagulate after exposure to hot exhaust. The additional space betweencations in the Ln-ZrO₂-based MMOSOs (e.g., Pr and Zr) furnished by thepresence of the Ln allows for easier and freer diffusion of oxygenthroughout the catalyst system (see, Example 8 and FIGS. 5-9).

Moreover, traditional support oxides such as alumina form a mixed phaseRh aluminate (locally) which essentially traps Rh in the Rh(III) state—aphenomenon which does not appreciably take place with Ln-ZrO₂-basedMMOSOs.

Finally, Rh present in catalyst systems with traditional support oxidesbecomes buried within the support oxide after exposure of the catalystsystem to high temperatures (i.e., aging). Burying the Rh has theunwanted effect of sequestering it from exhaust gases, thereby reducingthe ability of the catalyst sites to participate in conversion of theexhaust.

When catalyst systems of the present invention comprising aLn-ZrO₂-based MMOSO, such as Pr—ZrO₂-based MMOSO, are formulated with acertain amount of Rh, it has been found that such catalyst systemscontain higher amounts of initial Rh(0) immediately after formulation(i.e., fresh catalyst systems) when compared to catalyst systemscomprising traditional support oxides, such as La—Al₂O₃, formulated withthe same amount of starting Rh (see Example 5). Specifically, freshcatalyst systems comprising Rh and a Pr—ZrO₂-based MMOSO (i.e., freshlysynthesized and not aged through use) comprise more Rh(0) and reversibleRh₂O₃ than fresh catalyst systems comprising fresh Rh and La—Al₂O₃, eventhough the same amount of Rh was used during synthesis of the catalystsystem. Interestingly, even aged catalyst systems comprising Rh and aPr—ZrO₂-based MMOSO (i.e., aged under normal use conditions) comprisemore Rh(0) and reversible Rh₂O₃ than fresh catalysts comprising fresh Rhand La—Al₂O₃ (see Example 5).

After standard aging, none of the Rh(III)-MMO state is observed ineither the fresh or aged Rh/Pr—ZrO₂-based MMOSO catalysts.Comparatively, the fresh Rh/La—Al₂O₃ catalyst contains a measurableamount of the Rh(III)-MMO state and the aged Rh/La—Al₂O₃ catalystcontains significant amounts of the Rh(III)-MMO state (see Example 5).

Improved Light-Off Temperature

The light-off temperature of catalyst systems tends to rise (i.e.,worsen) after exposure of the catalyst system to high temperatures. Whencatalyst systems are present in, for example, catalytic converters, suchcompositions routinely operate under high-temperature conditions.Accordingly, catalyst systems with improved light-off temperatures areextremely useful in extending the lifetime of the catalyst. Thus, in oneaspect, the present invention refers to catalyst systems with improvedlight-off performance, even after high-temperature aging.

As discussed above, there have been several previous attempts atimproving the light-off performance of catalyst systems including:utilizing higher loadings of active precious metal catalysts (e.g., Rh);utilizing substrate structures with a higher channel density (and, thus,higher amounts of precious metal catalyst); utilizing a dual TWC systemcomprising a first close coupled catalyst and a second, larger, TWCcatalyst placed further away from the engine; and modifying the layoutof the PGM catalysts in CC TWC catalysts. As also discussed above, suchapproaches suffer from drawbacks including: increased cost due to use ofhigher amounts of precious metal catalysts; increase poisoning ofprecious metal catalysts; increased degradation of precious metalcatalysts due to exposure to higher temperatures; and decreases inexhaust and oxygen flow due to tighter packing of the catalysts systems.

The Ln-ZrO₂-based MMOSO catalyst systems of the present invention (suchas a La—ZrO₂-based or Pr—ZrO₂-based MMOSOs), have an improved (i.e.,lower) light-off temperature with respect to Rh catalyzed NO_(x)conversion. Thus, the catalyst systems of the present invention are ableto function efficiently without unnecessarily exposing the catalysts tohigh exhaust temperatures and without needing to increase the amount ofprecious metal catalyst used. For example, catalyst systems of thepresent invention comprising a washcoat and/or overcoat comprisingLa_(0.10)Zr_(0.90)O₂ or Pr_(0.10)Zr_(0.90)O₂ exhibited lower light-offtemperatures when compared to catalyst systems comprising 10% La—Al₂O₃(see Examples 3 and 6 and Table 5).

The improved (lower) light-off temperature is observed after typicalhigh-temperature in-use conditions. The lower light-off temperatures areespecially useful in improving catalyst efficiency when an engine isfirst engaged (i.e., a “cold start”) because the catalytic converter isstill at ambient temperature and is, thus, in a cold state.

Improved Conversion of Emission Byproducts

The catalyst systems of the present invention also exhibit improvedNO_(x) and hydrocarbon conversion efficiency in high-temperatureconditions. Such improvements are typically observed in the context ofRh-catalyzed NO_(x) and hydrocarbon conversion to nitrogen andCO₂/water, respectively Improvements in NO_(x) and hydrocarbonconversion aid in designing vehicles which meet strict emissionsstandards.

In particular, catalyst systems of the present invention which comprisea Ln-ZrO₂-based MMOSO exhibit improved Rh-catalyzed NO_(x) conversion atstandard and high engine operating temperatures as measured by both theFederal Test Procedure (“FTP”; standard operating temperature) and US06(high operating temperature) protocols. TWC catalyst systems withwashcoats comprising a) 40% OSM/30% La-Al₂O₃/30% Pr_(0.10)Zr_(0.90)O₂;or b) 40% OSM/60% Pr_(0.10)Zr_(0.90)O₂ exhibited improved Rh-catalyzedNO_(x) conversion when compared to catalyst systems comprising 40%OSM/60% La—Al₂O₃ (see Example 4 and Tables 2-3).

Further, catalyst systems with washcoats comprising a) 40% OSM/30%La-Al₂O₃/30% Pr_(0.10)Zr_(0.90)O₂; or b) 40% OSM/60%Pr_(0.10)Zr_(0.90)O₂ exhibit improved Rh-catalyzed non-methanehydrocarbon conversion when compared to TWC catalyst systems comprising40% OSM/60% La—Al₂O₃ (see Example 4 and Tables 2-3).

Improved Washcoat/Overcoat Structure

The Ln-ZrO₂-based MMOSO of the present invention improve the overallstructure of the washcoats or overcoats in which they are located.Without being bound by any particular theory, it is believed that thepresence of the lanthanide in the ZrO₂ structure stabilizes thetetragonal or cubic phases of ZrO₂ with respect to the monoclinic phase.It is believed that these tetragonal or cubic phases of ZrO₂ arearranged in a manner which permits faster and easier diffusion of oxygenthrough the catalyst structure enhancing the activity of the catalyst(see, Example 8 and FIGS. 5-8). In addition, the Ln, such as Pr or La,present in the Ln-ZrO₂-based MMOSO is present as solid solution—i.e., asolid solution of Ln exists with the Zr (see, Example 8 and FIG. 9).Because solid solutions are composed of a single homogenous phase, suchan arrangement also permits faster and easier diffusion of oxygenthrough the catalyst structure.

The effect of ease of oxygen diffusion appears to be mitigated as theamount of lanthanide present in the Ln-ZrO₂-based MMOSO increases beyonda certain point. For example, it has been found that doping of ZrO₂ with5%, 10% or 15% of Pr has the effect of stabilizing the ZrO₂ supportoxide in the tetragonal or cubic phases. However, the larger Pr³⁺cations (when compared to the Zr⁴⁺ cations) may act as steric barriersto oxygen diffusion as the amount of Pr increases.

Catalyst Systems Comprising Ln-ZrO₂-Based MMOSOs Overview

The catalyst systems (including TWC catalyst systems) of the presentinvention may have a variety of architectures. For example, a catalyticconverter system present in an automobile may contain both a CC catalystand an UF catalyst, wherein the CC catalyst is placed closer to theengine in comparison to the UF catalyst.

Both CC and/or UF catalysts typically comprise (1) a substrate, (2) awashcoat supported by the substrate, and (3) an optional overcoatsupported by the washcoat. In particular embodiments, the CC and/or UFcatalyst comprises (1) a substrate, (2) a washcoat supported by thesubstrate, and (3) an overcoat supported by the washcoat. In someembodiments of the present invention, the catalyst systems comprise CCand UF catalysts comprising a Ln-ZrO₂-based MMOSO. The Ln-ZrO₂-basedMMOSO may be present in either the washcoat, the overcoat, or both ofeither the CC catalyst, UF catalyst, or both.

In particular embodiments, the catalyst systems, whether present in theCC or UF catalysts, comprise (1) a substrate, (2) a washcoat, whereinthe washcoat is supported by the substrate, and (3) an overcoatcomprising a Ln-ZrO₂-based MMOSO, wherein the overcoat is supported bythe washcoat. In other embodiments, the catalyst systems, whetherpresent in the CC or UF catalysts, comprise (1) a substrate, (2) awashcoat comprising a Ln-ZrO₂-based MMOSO, wherein the washcoat issupported by the substrate, and (3) an overcoat, wherein the overcoat issupported by the washcoat. In yet other embodiments, the catalystsystems, whether present in the CC or UF catalysts, comprise (1) asubstrate, (2) a washcoat comprising a Ln-ZrO₂-based MMOSO, wherein thewashcoat is supported by the substrate, and (3) an overcoat comprising aLn-ZrO₂-based MMOSO, wherein the overcoat is supported by the washcoat.

Substrates

A variety of materials are appropriate as substrates for the presentinvention. For example, the substrate may be a refractive material, aceramic substrate, a honeycomb structure, a metallic substrate, aceramic foam, a metallic foam, a reticulated foam, or suitablecombinations, where the substrate has a plurality of channels and atleast the required porosity. As is known in the art, the number ofchannels present may vary depending upon the substrate used. It ispreferred that the substrate offer a three-dimensional supportstructure.

The substrate may be in the form of beads or pellets. In suchembodiments, the beads or pellets may be formed from, for example,alumina, silica alumina, silica, titania, mixtures thereof, or anysuitable material. In a particular embodiment, the substrate may be ahoneycomb substrate, for example a ceramic honeycomb substrate or ametal honeycomb substrate. The ceramic honeycomb substrate may be formedfrom, for example, sillimanite, zirconia, petalite, spodumene (lithiumaluminum silicate), magnesium silicates, mullite, alumina, cordierite,other alumino-silicate materials, silicon carbide, aluminum nitride, orcombinations thereof. Other ceramic substrates would be apparent to oneof ordinary skill in the art.

In embodiments wherein the substrate is a metal honeycomb substrate, themetal may be, for example, a heat-resistant base metal alloy,particularly an alloy in which iron is a substantial or major component.In addition, metal substrate surface may be oxidized at elevatedtemperatures (e.g., above about 1000° C.) to improve the corrosionresistance of the alloy by forming an oxide layer on the surface of thealloy. This oxide layer on the surface of the alloy may also enhance theadherence of a washcoat to the surface of the monolith substrate.

In one embodiment, the substrate may be a monolithic carrier having aplurality of fine, parallel flow passages extending through themonolith. Such passages may be of any suitable cross-sectional shapeand/or size. For example, such passages may be trapezoidal, rectangular,square, sinusoidal, hexagonal, oval, or circular, although other shapesare also suitable. The monolith may contain from about 9 to about 1200or more gas inlet openings or passages per square inch of cross section,although fewer passages may be used.

Washcoats and Overcoats

The washcoats and overcoats of the catalyst systems of the presentinvention typically comprise, inter alia, a metal catalyst, an OSM, anda support oxide—each of which is described herein. In some embodiments,the washcoats may further comprise additives which aid in retardingmetal catalyst poisoning.

One aspect of the present invention is the replacement of an amount ofthe traditional support oxide typically present in the overcoat orwashcoat by an amount of Ln-ZrO₂-based MMOSO, such as a La—ZrO₂-basedMMOSO or Pr—ZrO₂-based MMOSO. In some embodiments, an amount of thetraditional support oxide typically present in the overcoat is replacedwith an amount of Ln-ZrO₂-based MMOSO, as described herein. In someembodiments, an amount of the traditional support oxide typicallypresent in the washcoat is replaced with an amount of Ln-ZrO₂-basedMMOSO, as described herein. In other embodiments, an amount of thetraditional support oxide typically present in the both the washcoat andovercoat is replaced with an amount of Ln-ZrO₂-based MMOSO, as describedherein.

In some embodiments the washcoats and overcoats of the catalyst systemsof the present invention can be used in conjunction with an OSM made bythe Improved Wet Chemical Process (IWCP) (see, Example 10 and FIG. 16)or the High Temperature Process (HTP) (see, Example 11).

Metal Catalysts

The metal catalysts present in the catalyst systems of the invention aretypically present in the washcoat and/or overcoat (if one is present).Metal catalysts useful for the present invention include PGM, zirconia,alumina or lanthanide catalysts. The washcoat and overcoat may containthe same metal catalyst or different metal catalysts. In addition, thewashcoat and overcoat may contain the same combination of metalcatalysts (e.g., both contain metal catalysts “A” and “B”) or differentcombinations of catalysts (e.g., the washcoat contains metal catalysts“A” and “B” while the substrate contains metal catalysts “C” and “D”).

In some embodiments, the metal catalysts used are PGM catalysts—i.e.,Ru, Rh, Pd, Os, Ir, Pt, or combinations thereof. In some embodiments,the metal catalysts used are Rh, Pd, Pt, or combinations thereof.

In particular, Rh plays a critical role in the TWC process with respectto the conversion of nitrogen oxides (NO_(x)) to nitrogen and oxygen,and of hydrocarbons to carbon dioxide and water. As emissions standardstighten (specifically NO_(x) emissions) the tendency is to use higheramounts of expensive Rh metal oxides in catalysts in order to meet suchstandards. This is especially problematic for catalytic converters usedin engines wherein NO_(x) emissions (so-called engine-out emissions) areparticularly high. Further, in order for new vehicles to meet CARB(California Air Resources Board) and EPA (Environmental ProtectionAgency) tailpipe regulations, NO_(x) conversion efficiencies mustgenerally be in excess of 95% and, in some cases, higher than 99%.

Accordingly, in one aspect, the present invention provides catalystsystems comprising Rh and a Ln-ZrO₂-based MMOSO. In one embodiment, thewashcoat of a catalyst system comprises Rh and a Ln-ZrO₂-based MMOSO. Inanother embodiment, the overcoat of a catalyst system comprises Rh and aLn-ZrO₂-based MMOSO. In yet another embodiment, the washcoat andovercoat of a catalyst system comprises Rh and a Ln-ZrO₂-based MMOSO. Insome embodiments, the catalyst systems of the present invention arepresent in TWC catalysts. In other embodiments, the catalyst systems ofthe present invention are present in catalytic converters.

Oxygen Storage Materials

Catalytic converters may be exposed to exhaust that is either rich(contains a high amount of unburnt fuel compared to oxygen) or lean(contains a low amount of unburnt fuel compared to oxygen). Oxygenstorage materials (OSMs) supply oxygen to rich exhaust and take upoxygen from lean exhaust, buffering the catalyst systems against thefluctuating supply of oxygen and, in turn, increasing catalystefficiency. Thus, oxygen storage materials present in, for example, TWCcatalyst systems, allow the conversion efficiency of the catalyst systemto remain relatively constant even in the face of varying inlet air/fuelratios. OSMs may be comprised of zirconia, lanthanides, alkaline earthmetals, transition metals, cerium oxide materials, or mixtures thereof.The use of cerium oxide in catalytic converters is described in“Critical Topics in Exhaust Gas Treatment” (Research Studies Press Ltd,Baldock, Hertfordshire, England, 2000), which is incorporated herein byreference in its entirety.

In some embodiments the OSM has a composition according to the formula:

Ce_(1-a-b-c-d)D_(a)E_(b)F_(c)Zr_(d)O₂,

wherein:

-   -   a, b and c may be, independently, 0-0.7;    -   d may be 0-0.9; and    -   D, E and F may be, independently, selected from the group        consisting of lanthanides, alkaline earth metals and transition        metals.

In some embodiments, D is Nd and a may be 0.01-0.20, 0.01-0.15,0.01-0.10, 0.02-0.08, 0.03-0.07, or 0.04-0.06. In a particularembodiment, D is Nd and a=0.05.

In some embodiments, E is Pr and b may be 0.01-0.20, 0.01-0.15,0.01-0.10, 0.02-0.08, 0.03-0.07, or 0.04-0.06. In a particularembodiment, E is Pr and b=0.05.

In some embodiments, c=0.

In some embodiments, d may be 0.2-0.8, 0.3-0.7, 0.4-0.7, 0.5-0.7, or0.55-0.65. In a particular embodiment, d=0.6.

In a particular embodiment, the OSM of the present invention has thefollowing formula: Ce_(0.3)Nd_(0.05)Pr_(0.05)Zr_(0.6)O₂.

In some embodiments, the OSM constitutes about 1%, 2%, 3%, 4%, 5%, 6%,7%, 8%, 9%, 10%, 11%, 12%, 13%, 14%, 15%, 16%, 17%, 18%, 19%, 20%, 21%,22%, 23%, 24%, 25%, 26%, 27%, 28%, 29%, 30%, 31%, 32%, 33%, 34%, 35%,36%, 37%, 38%, 39%, 40%, 41%, 42%, 43%, 44%, 45%, 46%, 47%, 48%, 49%,50%, 51%, 52%, 53%, 54%, 55%, 56%, 57%, 58%, 59%, 60%, 61%, 62%, 63%,64%, 65%, 66%, 67%, 68%, 69% 70%, 71%, 72%, 73%, 74%, 75%, 76%, 77%,78%, 79%, 80%, 81%, 82%, 83%, 84%, 85%, 86%, 87%, 88%, 89%, 90%, 91%,92%, 93%, 94%, 95%, 96%, 97%, 98%, 99% or 100% of the total weight ofthe washcoat and/or overcoat. In one embodiment, the OSM constitutesabout 20-60% of the total weight of the washcoat and/or overcoat. Inanother embodiment, the OSM constitutes about 30-50% of the total weightof the washcoat and/or overcoat. In yet another embodiment, the OSMconstitutes about 39-41%, 38-42%, 37-43%, 36-44%, or 35-45% of the totalweight of the washcoat and/or overcoat. In one embodiment, the OSMconstitutes about 40%, 80% or 100% of the total weight of the washcoatand/or overcoat. In one embodiment, the OSM constitutes 40%, 80% or 100%of the total weight of the washcoat and/or overcoat.

In some embodiments, the OSM constitutes up to about 1%, 2%, 3%, 4%, 5%,6%, 7%, 8%, 9%, 10%, 11%, 12%, 13%, 14%, 15%, 16%, 17%, 18%, 19%, 20%,21%, 22%, 23%, 24%, 25%, 26%, 27%, 28%, 29%, 30%, 31%, 32%, 33%, 34%,35%, 36%, 37%, 38%, 39%, 40%, 41%, 42%, 43%, 44%, 45%, 46%, 47%, 48%,49%, 50%, 51%, 52%, 53%, 54%, 55%, 56%, 57%, 58%, 59%, 60%, 61%, 62%,63%, 64%, 65%, 66%, 67%, 68%, 69% 70%, 71%, 72%, 73%, 74%, 75%, 76%,77%, 78%, 79%, 80%, 81%, 82%, 83%, 84%, 85%, 86%, 87%, 88%, 89%, 90%,91%, 92%, 93%, 94%, 95%, 96%, 97%, 98%, 99% or 100% of the total weightof the washcoat and/or overcoat. In one embodiment, the OSM constitutesup to about 20-60% of the total weight of the washcoat and/or overcoat.In another embodiment, the OSM constitutes up to about 30-50% of thetotal weight of the washcoat and/or overcoat. In yet another embodiment,the OSM constitutes up to about 39-41%, 38-42%, 37-43%, 36-44%, or35-45% of the total weight of the washcoat and/or overcoat. In oneembodiment, the OSM constitutes up to about 40%, 80% or 100% of thetotal weight of the washcoat and/or overcoat. In one embodiment, the OSMconstitutes up to 40%, 80% or 100% of the total weight of the washcoatand/or overcoat.

Support Oxides

Support oxides are, generally, porous solid oxides which are used toprovide a high surface area which aids in oxygen distribution andexposure of catalysts to reactants such as NO_(x), CO, and hydrocarbons.Support oxides are normally stable at high temperatures as well as at arange of reducing and oxidizing conditions. Metal catalysts present inthe washcoat, overcoat (if one is present), or both, are typicallysupported by support oxides.

The amount of support oxide present in a catalyst system may varydepending on where in the system the support oxide is present. In someembodiments, the washcoat and overcoat (if one is present) of a catalystsystem may contain the same amount of support oxide. In otherembodiments, the washcoat and overcoat (if one is present) of a catalystsystem may contain different amounts of support oxide.

Compounds used in traditional support oxides include, but are notlimited to, gamma-alumina, ceria-based powders, or any mixture oftitania, silica, alumina (transition and alpha-phase), ceria, zirconia,Ce_(1-α)Zr_(α)O₂, and any possible doped ceria formulations. Atransition phase is a meta-stable phase of alumina (beta, gamma, theta,delta) that transforms to the stable alpha-alumina with sufficient timeand temperature. In a preferred embodiment, the support oxide isalumina.

Modifiers may optionally be added to the alumina to retard undesiredphase transitions of the alumina from the gamma phase to the alpha phasewhen the alumina is exposed to elevated temperatures—i.e., to stabilizethe alumina. Examples of suitable modifiers (or thermal stabilizers)include, for example, rare earth oxides, silicon oxides, oxides of GroupIVB metals (zirconium, hafnium, or titanium), alkaline earth oxides, orcombinations thereof. Alumina is typically utilized in the washcoat as ahigh surface area carrier solid or support and is referred to as “gammaalumina” or “activated alumina.” Suitable alumina compositions generallyhave a BET (Brunauer, Emmett and Teller) surface area of 60 m²/g or moreand, often, about 200 m²/g or more.

Specific examples of suitable stabilizing agents include lanthanideoxides (Ln₂O₃) and/or strontium oxide (SrO). Such lanthanide- andstrontium-based stabilizing agents are typically added to support oxides(e.g., alumina) as a solution of lanthanide nitrate, strontium nitrate,or mixtures thereof. Heating or calcining the lanthanide nitrate and/orstrontium nitrate then forms the desired oxide. A particular example ofa useful stabilized alumina is La—Al₂O₃.

In one aspect, the present invention improves upon catalyst systems byreplacing an amount of the traditional alumina support oxide with anamount of the Ln-ZrO₂-based MMOSOs of the present invention. In someembodiments, the Ln-ZrO₂-based MMOSOs of the present invention areutilized in the washcoat of the catalyst systems. In other embodiments,the Ln-ZrO₂-based MMOSOs are utilized in the overcoat of the catalystsystem, if an overcoat is present. In yet other embodiments, theLn-ZrO₂-based MMOSOs are in utilized both the washcoat and the overcoatof the catalyst system, if an overcoat is present. In some embodiments,the Ln-ZrO₂-based MMOSOs is utilized in a layer wherein Rh is present,

Any of the metal catalysts described above may be used in combinationwith the Ln-ZrO₂-based MMOSOs. As noted, the support oxides of thepresent invention have a particularly beneficial impact on Rh lifetimeand efficiency. However, metal catalysts such Rh, Pd, Pt, orcombinations thereof, may be used in catalyst systems comprisingLn-ZrO₂-based MMOSOs.

The amount of traditional alumina support oxide in the washcoat and/orovercoat replaced with an amount of Ln-ZrO₂-based MMOSO, such asLa-ZrO₂-based MMOSO or Pr—ZrO₂-based MMOSO, can vary. Thus, in oneembodiment, about 1%, 2%, 3%, 4%, 5%, 6%, 7%, 8%, 9%, 10%, 11%, 12%,13%, 14%, 15%, 16%, 17%, 18%, 19%, 20%, 21%, 22%, 23%, 24%, 25%, 26%,27%, 28%, 29%, 30%, 31%, 32%, 33%, 34%, 35%, 36%, 37%, 38%, 39%, 40%,41%, 42%, 43%, 44%, 45%, 46%, 47%, 48%, 49%, 50%, 51%, 52%, 53%, 54%,55%, 56%, 57%, 58%, 59%, 60%, 61%, 62%, 63%, 64%, 65%, 66%, 67%, 68%,69%, 70%, 71%, 72%, 73%, 74%, 75%, 76%, 77%, 78%, 79%, 80%, 81%, 82%,83%, 84%, 85%, 86%, 87%, 88%, 89%, 90%, 91%, 92%, 93%, 94%, 95%, 96%,97%, 98%, 99% or 100% of the traditional alumina is replaced with acorresponding amount of Ln-ZrO₂-based MMOSO. In other embodiments, about10%, 20%, 30%, 40%, 50%, 60%, 70%, 80%, 90% or 100% of the traditionalalumina is replaced with a corresponding amount of Ln-ZrO₂-based MMOSO.In yet other embodiments, about 10%, 50% or 100% of the traditionalalumina is replaced with a corresponding amount of Ln-ZrO₂-based MMOSO.In a particular embodiment, about 50% or about 100% of the traditionalalumina is replaced with a corresponding amount of Ln-ZrO₂-based MMOSO.In another particular embodiment, 50% or 100% of the traditional aluminais replaced with a corresponding amount of Ln-ZrO₂-based MMOSO.

In some embodiments, about 10-90%, 20-80%, 30-70%, 40-60%, 45-55%,80-100%, 90-100%, or 95-100% of the traditional alumina is replaced witha corresponding amount of Ln-ZrO₂-based MMOSO. In other embodiments,about 49-51%, 48-52%, 47-53%, 46-54%, 91-100%, 92-100%, 93-100%,94-100%, 95-100%, 96-100%, 97-100%, 98-100%, or 99-100% of thetraditional alumina is replaced with a corresponding amount ofLn-ZrO₂-based MMOSO.

In some embodiments, up to about 1%, 2%, 3%, 4%, 5%, 6%, 7%, 8%, 9%,10%, 11%, 12%, 13%, 14%, 15%, 16%, 17%, 18%, 19%, 20%, 21%, 22%, 23%,24%, 25%, 26%, 27%, 28%, 29%, 30%, 31%, 32%, 33%, 34%, 35%, 36%, 37%,38%, 39%, 40%, 41%, 42%, 43%, 44%, 45%, 46%, 47%, 48%, 49%, 50%, 51%,52%, 53%, 54%, 55%, 56%, 57%, 58%, 59%, 60%, 61%, 62%, 63%, 64%, 65%,66%, 67%, 68%, 69%, 70%, 71%, 72%, 73%, 74%, 75%, 76%, 77%, 78%, 79%,80%, 81%, 82%, 83%, 84%, 85%, 86%, 87%, 88%, 89%, 90%, 91%, 92%, 93%,94%, 95%, 96%, 97%, 98%, 99% or 100% of the traditional alumina isreplaced with a corresponding amount of Ln-ZrO₂-based MMOSO. In otherembodiments, up to about 10%, 20%, 30%, 40%, 50%, 60%, 70%, 80%, 90% or100% of the traditional alumina is replaced with a corresponding amountof Ln-ZrO₂-based MMOSO. In yet other embodiments, up to about 10%, 50%or 100% of the traditional alumina is replaced with a correspondingamount of Ln-ZrO₂-based MMOSO. In a particular embodiment, up to about50% or about 100% of the traditional alumina is replaced with acorresponding amount of Ln-ZrO₂-based MMOSO. In another particularembodiment, up to 50% or 100% of the traditional alumina is replacedwith a corresponding amount of Ln-ZrO₂-based MMOSO.

In some embodiments, up to about 10-90%, 20-80%, 30-70%, 40-60%, 45-55%,80-100%, 90-100%, or 95-100% of the traditional alumina is replaced witha corresponding amount of Ln-ZrO₂-based MMOSO. In other embodiments, upto about 49-51%, 48-52%, 47-53%, 46-54%, 91-100%, 92-100%, 93-100%,94-100%, 95-100%, 96-100%, 97-100%, 98-100%, or 99-100% of thetraditional alumina is replaced with a corresponding amount ofLn-ZrO₂-based MMOSO.

The Ln-ZrO₂-based MMOSO of the catalyst systems of the presentinvention, such as La—ZrO₂-based MMOSO or Pr—ZrO₂-based MMOSO, mayconstitute about 1%, 2%, 3%, 4%, 5%, 6%, 7%, 8%, 9%, 10%, 11%, 12%, 13%,14%, 15%, 16%, 17%, 18%, 19%, 20%, 21%, 22%, 23%, 24%, 25%, 26%, 27%,28%, 29%, 30%, 31%, 32%, 33%, 34%, 35%, 36%, 37%, 38%, 39%, 40%, 41%,42%, 43%, 44%, 45%, 46%, 47%, 48%, 49%, 50%, 51%, 52%, 53%, 54%, 55%,56%, 57%, 58%, 59%, 60%, 61%, 62%, 63%, 64%, 65%, 66%, 67%, 68%, 69%,70%, 71%, 72%, 73%, 74%, 75%, 76%, 77%, 78%, 79%, 80%, 81%, 82%, 83%,84%, 85%, 86%, 87%, 88%, 89%, 90%, 91%, 92%, 93%, 94%, 95%, 96%, 97%,98% or 99% of the washcoat, and/or the overcoat (if one is present) byweight. In some embodiments, the Ln-ZrO₂-based MMOSO constitutes about5-60%, 10-50%, 20-40%, 20-80%, 40-80%, or 50-70% of the washcoat and/orthe overcoat (if one is present), by weight. In other embodiments, theLn-ZrO₂-based MMOSO constitutes about 29-31%, 28-32%, 27-33%, 26-34%,25-35%, 59-61%, 58-62%, 57-63%, 56-64% or 55-65% of the washcoat. Inother embodiments, the Ln-ZrO₂-based MMOSO constitutes about 30% or 60%of the washcoat. In one embodiment, the Ln-ZrO₂-based MMOSO ofconstitutes 30% or 60% of the washcoat.

The Ln-ZrO₂-based MMOSO of the catalyst systems of the present inventionsuch as La—ZrO₂-based MMOSO or Pr—ZrO₂-based MMOSO, may also constituteup to about 1%, 2%, 3%, 4%, 5%, 6%, 7%, 8%, 9%, 10%, 11%, 12%, 13%, 14%,15%, 16%, 17%, 18%, 19%, 20%, 21%, 22%, 23%, 24%, 25%, 26%, 27%, 28%,29%, 30%, 31%, 32%, 33%, 34%, 35%, 36%, 37%, 38%, 39%, 40%, 41%, 42%,43%, 44%, 45%, 46%, 47%, 48%, 49%, 50%, 51%, 52%, 53%, 54%, 55%, 56%,57%, 58%, 59%, 60%, 61%, 62%, 63%, 64%, 65%, 66%, 67%, 68%, 69%, 70%,71%, 72%, 73%, 74%, 75%, 76%, 77%, 78%, 79%, 80%, 81%, 82%, 83%, 84%,85%, 86%, 87%, 88%, 89%, 90%, 91%, 92%, 93%, 94%, 95%, 96%, 97%, 98% or99% of the washcoat, and/or the overcoat (if one is present) by weight.In some embodiments, the Ln-ZrO₂-based MMOSO constitutes up to about5-60%, 10-50%, 20-40%, 20-80%, 40-80%, or 50-70% of the washcoat and/orthe overcoat (if one is present), by weight. In other embodiments, theLn-ZrO₂-based MMOSO constitutes up to about 29-31%, 28-32%, 27-33%,26-34%, 25-35%, 59-61%, 58-62%, 57-63%, 56-64% or 55-65% of thewashcoat. In other embodiments, the Ln-ZrO₂-based MMOSO constitutes upto about 30% or 60% of the washcoat. In one embodiment, theLn-ZrO₂-based MMOSO of constitutes up to 30% or 60% of the washcoat.

Additives

The washcoats and overcoats of the catalyst systems of the presentinvention may contain additives which aid in retarding the poisoning ofprecious metal catalysts by phosphorus and sulfur. Consumption of enginelubricants results in the generation of phosphorus and, in turn, thepoisoning and deactivation of precious metal catalysts. Thus, additivessuch as calcium, barium, lanthanides and/or cerium may be added to thewashcoats and/or overcoats (if present) as a means of retarding thepoisoning process. In some embodiments, the additive is CaCO₃, La₂O₃ orBaCO₃. In a particular embodiment, the additive is BaCO₃. It is notedthat, upon exposure to exhaust containing, for example phosphorous,CaCO₃, La₂O₃ and BaCO₃ are converted to Ca₃(PO₄)₂, LaPO₄ and Ba₃(PO₄)₂,respectively.

Amounts of such additives suitable for use in catalyst systems are wellknown in the art.

Catalyst Systems Comprising Lanthanide Doped Support Oxides

Accordingly, the washcoats and/or overcoats of the present inventioncomprise, inter alia, by weight: a % of OSM; a % of traditional supportoxide, and a % of Ln-ZrO₂-based MMOSO. In particular embodiments, thecatalyst systems of the present invention comprise, by weight: a % ofCe-based OSM; a % of Al₂O₃ or La—Al₂O₃; and a % ofPr_(X %)Zr_((1-X) %)O₂, as described herein. In some embodiments, thecatalyst systems of the present invention comprise, by weight: 40% ofCe-based OSM; 30% Al₂O₃ or La—Al₂O₃; and 30% of Pr_(X %)Zr_((1-X) %)O₂,as described herein. In other embodiments, the catalyst systems of thepresent invention comprise, by weight: 40% of Ce-based OSM; and 60% ofPr_(X %)Zr_((1-X) %)O₂, as described herein. In a particular embodiment,the catalyst systems of the present invention comprise: 40%(Ce_(0.3)Nd_(0.05)Pr_(0.05) Zr_(0.6)O₂); 30% (La—Al₂O₃); and 30%(Pr_(X %)Zr_((1-X) %)O₂) (i.e., 50% of the traditional alumina isreplaced with Pr_(X %)Zr_((1-X) %)O₂). In another particular embodiment,the catalyst systems of the present invention comprise: 40%(Ce_(0.3)Ncl_(0.05)Pr_(0.05) Zr_(0.6)O₂); and 60% ofPr_(X %)Zr_((1-X) %)O₂ (i.e., 100% of the traditional alumina isreplaced with Pr_(X %)Zr_((1-X) %)O₂). As discussed herein, in suchembodiments, X can be, for example, 5%, 10% or 15%. In addition, asdiscussed herein, such OSM/support oxides may be in the washcoat,overcoat, or both.

In other particular embodiments, the catalyst systems of the presentinvention comprise, by weight: % of Ce-based OSM; a % of Al₂O₃ orLa—Al₂O₃; and a % of La_(X %)Zr_((1-X) %)O₂, as described herein. Insome embodiments, the catalyst systems of the present inventioncomprise, by weight: 40% of Ce-based OSM; 30% Al₂O₃ or La—Al₂O₃; and 30%of La_(X %)Zr_((1-X) %)O₂, as described herein. In other embodiments,the catalyst systems of the present invention comprise, by weight: 40%of Ce-based OSM; and 60% of La_(X %)Zr_((1-X) %)O₂, as described herein.In a particular embodiment, the catalyst systems of the presentinvention comprise: 40% (Ce_(0.3)Nd_(0.05) La_(0.05) Zr_(0.6)O₂); 30%(La—Al₂O₃); and 30% (La_(X %)Zr_((1-X) %)O₂) (i.e., 50% of thetraditional alumina is replaced with La_(X %)Zr_((1-X) %)O₂). In anotherparticular embodiment, the catalyst systems of the present inventioncomprise: 40% (Ce_(0.3)Nd_(0.05) La_(0.05) Zr_(0.6)O₂); and 60% ofLa_(X %)Zr_((1-X) %)O₂ (i.e., 100% of the traditional alumina isreplaced with La_(X %)Zr_((1-X) %)O₂). As discussed herein, in suchembodiments, X can be, for example, 5%, 10% or 15%. In addition, asdiscussed herein, such OSM/support oxides may be in the washcoat,overcoat, or both.

In a particular embodiment the catalyst system comprises a washcoat andan overcoat as follows. The washcoat, loaded at 180 g/L, comprisesLa—Al₂O₃ and an OSM (30% CeO₂, 60% ZrO₂, 5% Nd₂O₃ and 5% Pr₆O₁₁) in aratio of 1.5:1 (by weight). The washcoat is impregnated with Pd to givea final Pd loading in the washcoat of about 139.3 g/ft³. Barium is alsoimpregnated into the washcoat to give a Pd:Ba ratio of 1:6. The overcoat(loaded onto the washcoat at 60 g/L) comprises(Pr_(0.10)Zr_(0.90)O₂):(30% CeO₂, 60% ZrO₂, 5% Nd₂O₃, 5% Pr₆O₁₁) in aratio of 1.5:1 (by weight) with a Rh loading of 10.71 g/ft³.

Methods of Making Catalysts Methods of Making LnZrO₂-Based Catalysts

In yet another aspect, the present invention relates to methods ofmaking the Ln-ZrO₂-based MMOSOs disclosed herein.

Washcoat and overcoats comprising Ln-ZrO₂-based MMOSOs can generally bemade using the techniques exemplified in Example 2.

In addition, catalyst systems comprising Ln-ZrO₂-based MMOSOs, such asPr—ZrO₂-based MMOSOs or La—ZrO₂-based MMOSOs, can be made as follows.For example, a catalyst system which comprises a substrate and washcoatcan be generated by: a) depositing a washcoat comprising a Ln-ZrO₂-basedMMOSO, an OSM and a metal catalyst on a substrate; and b) treating thewashcoat and substrate by drying and calcination. Alternatively, acatalyst system which comprises a substrate and washcoat can begenerated by: a) depositing a washcoat comprising a Ln-ZrO₂-based MMOSOand an OSM on a substrate; b) treating the washcoat and substrate bycalcination; and c) impregnating a metal catalyst into the washcoat,followed by drying and calcination.

In some embodiments, the catalyst system comprises a substrate, awashcoat and an overcoat. Such catalyst systems can be generated by: a)depositing a washcoat comprising a Ln-ZrO₂-based MMOSO, an OSM and ametal catalyst on a substrate; b) treating the washcoat and substrate bycalcination; c) depositing an overcoat onto the washcoat, wherein theovercoat comprises a support oxide, an OSM and a metal catalyst,followed by drying and calcination. Alternatively, the catalyst systemcan be generated by: a) depositing a washcoat comprising a Ln-ZrO₂-basedMMOSO and an OSM on a substrate; b) treating the washcoat and substrateby calcination; c) impregnating a metal catalyst into the washcoat; d)depositing an overcoat onto the washcoat, wherein the overcoat comprisesa support oxide, an OSM and a metal catalyst; and e) impregnating ametal catalyst into the overcoat, followed by drying and calcination.The same methods are suitable for generating catalyst systems whereinthe washcoat comprises a support oxide, an OSM and a catalyst and theovercoat comprises a Ln-ZrO₂-based MMOSO, an OSM and a catalyst. Inaddition, the same methods can be used to generate catalyst systemswherein both the washcoat and overcoat comprise a Ln-ZrO₂-based MMOSO,an OSM and a catalyst.

In embodiments wherein the metal catalyst is mixed with the washcoatand/or overcoat (typically present as a slurry) or impregnated into anovercoat and/or washcoat, the metal catalyst may be added in the form ofa nitrate, acetate or chloride salt. In embodiments wherein the metalcatalyst is impregnated into an overcoat and/or washcoat, the metalcatalyst may be impregnated as an aqueous solution.

Methods of Utilizing Catalysts of the Present Invention

Catalyst systems comprising the Ln-ZrO₂-based MMOSOs of the presentinvention, such as Pr—ZrO₂-based MMOSO or La—ZrO₂-based MMOSO, areuseful for a variety of purposes. As discussed herein, the Ln-ZrO₂-basedMMOSOs may be used in catalytic converter systems present in, forexample, automobiles.

In some embodiments, catalyst systems comprising Ln-ZrO₂-based MMOSOs,such as Pr—ZrO₂-based MMOSO or La—ZrO₂-based MMOSO, are used to reducetoxic exhaust gas emissions. Accordingly, the present inventionenvisions a method of reducing toxic gas emissions comprising contactingthe gas emissions with catalyst systems comprising Ln-ZrO₂-based MMOSOs.The present invention also refers to a method of reducing toxic gasemissions by utilizing catalyst systems comprising Ln-ZrO₂-based MMOSOs.

As discussed herein, catalyst systems comprising Ln-ZrO₂-based MMOSOs,such as Pr—ZrO₂-based MMOSO or La—ZrO₂-based MMOSO, exhibit increasedoxygen flow when compared to catalyst systems comprising traditionalsupport oxides. Thus, the present invention also refers to a method ofincreasing oxygen flow through a catalytic system by stabilizing thephase of the support oxide present in the system, preferably stabilizingthe tetragonal phase. The tetragonal phase can be stabilized by usingLn-ZrO₂-based MMOSOs in catalyst systems.

Catalyst systems comprising Ln-ZrO₂-based MMOSOs, such as Pr—ZrO₂-basedMMOSO or La—ZrO₂-based MMOSO, also exhibit improved catalystlifetime—particularly Rh lifetime. Thus, the present inventioncontemplates methods of improving the lifetime of a catalyst systemcomprising a metal catalyst such as Rh by utilizing a washcoat,overcoat, or both comprising a Ln-ZrO₂-based MMOSO in a catalyst system.Such methods include: a) reducing the amount of metal catalystdeactivated during the aging of the catalyst system; b) increasing theamount of metallic catalyst (e.g., Rh(0)) initially present in thecatalyst system; or c) both a) and b). In addition, such methodsinclude: a) increasing the amount of Rh(0) and/or Rh(III) as Rh₂O₃initially present in the catalyst system; or b) decreasing the amount ofRh(0) which is converted to Rh(III) as Rh₂O₃ or Rh(III)-MMO during agingof the catalyst system.

Catalyst systems comprising Ln-ZrO₂-based MMOSOs, such as Pr—ZrO₂-basedMMOSO or La—ZrO₂-based MMOSO, can also be used in methods of improvingTWC. For example, the present invention includes methods of improvingTWC of gas emissions comprising contacting the gas emissions withcatalyst systems comprising Ln-ZrO₂-based MMOSOs. The present inventionalso refers to methods of improving TWC of gas emissions by utilizingcatalyst systems comprising Ln-ZrO₂-based MMOSOs.

These and other embodiments of the invention may be further illustratedin the following non-limiting Examples.

EXAMPLES Example 1 Generation of Washcoats and Overcoats ComprisingTraditional Support Oxides

The following is a representative protocol for the production ofwashcoats and overcoats comprising traditional support oxides. Suchwashcoats and overcoats can be used in combination with washcoats andovercoats comprising the Ln-ZrO₂-based MMOSOs of the present invention.The protocols in this Example represent standard techniques known in theart (see, for example, U.S. Pat. No. 7,641,875).

Traditional washcoats were generated as follows. A slurry comprising theOSM, alumina powder and lanthanide nitrate solution (commerciallyavailable as lanthanum nitrate product code 5248 from Molycorp, Inc.,Mountain Pass, Calif.) in deionized water was generated. The slurry wasthen milled in a Szegvari Type IS Atrittor until the rheology wassuitable for coating the support. A cordierite honeycomb support wasdipped into the slurry. Excess slurry was blown from the support with anair jet. The support was dried in flowing air at room temperature, washeat-treated in air at about 150° C., and was calcined at 750° C. for 4hours to yield a MPC composition.

Traditional overcoats were generated using the process described inExample 2, except that La—Al₂O₃ was used instead of 10% Pr—ZrO₂-basedMMOSO.

Example 2 Generation of Overcoats Comprising Doped ZrO₂-Based MMOSOs

A 10% Pr—ZrO₂-based MMOSO overcoat was generated using the followingprocedure. This procedure can generally be used to generate overcoatscontaining Ln-ZrO₂-based MMOSOs.

A 10% Pr—ZrO₂-based MMOSO/Ce_(0.3)Zr_(0.6)Nd_(0.05)Y_(0.05)O₂ (OSM)(1.5:1 ratio) overcoat slurry containing 38% solid (by weight) wasgenerated as follows. The appropriate amount of 10% Pr—ZrO₂,Ce_(0.3)Zr_(0.6)Nd_(0.05)Y_(0.05)O₂, and de-ionized water were weighedout in separate containers. The 10% Pr—ZrO₂ andCe_(0.3)Zr_(0.6)Nd_(0.05)Y_(0.05)O₂ were weighed out in a 1.5:1 ratio.Acetic acid (0.5% relative to the solids) was weighed and then added tothe de-ionized water container. The above reactants were then combinedinto an attrition-mill as follows: 1) 75-80% of the de-ionized water andacetic acid solution was added; 2) the 10% Pr—ZrO₂ and theCe_(0.3)Zr_(0.6)Nd_(0.05)Y_(0.05)O₂ were added; 3) the remainingde-ionized water and acetic acid solution was added. The resultingslurry was then milled until homogenous. Once the 10% Pr—ZrO₂-basedMMOSO/OSM slurry particle size reached d(50) 5±0.5 (4.5 target)micrometers, the milled slurry was dropped into a container and thefinal pH and % solids were recorded.

The resulting 10% Pr—ZrO₂-basedMMOSO/Ce_(0.3)Zr_(0.6)Nd_(0.05)Y_(0.05)O₂ milled slurry was thenmetalized with Rh as follows. The milled slurry was mixed with a highshear mixer. The solid (%) content of the milled slurry was thenmeasured in a moisture balance and the initial pH recorded. Theappropriate amounts of 10% Pr—ZrO₂-basedMMOSO/Ce_(0.3)Zr_(0.6)Nd_(0.05)Y_(0.05)O₂ milled slurry, Rh(NO₃)₃solution, and de-ionized water were then measured in separatecontainers. To generate a concentration of 20 g/ft³ Rh in the overcoat,an Rh slurry concentration of 1.177% (by weight) was required. Using thehigh sheer mixer, the Rh(NO₃)₃ solution was added to the 10%Pr—ZrO₂-based MMOSO/OSM milled slurry and mixed until homogenous. The pHof the resulting slurry was then recorded. The resulting slurry wasadjusted to a pH of 6.4 using ammonium hydroxide. The previously weighedde-ionized water was then added to the metalized slurry and the pH wasconfirmed to remain at a pH of 6.4 (note that, if the pH was not at 6.4,it would have been adjusted to pH 6.4). The final viscosity range was75-200 cp@60 rpm (generally, the target viscosity is 120 cp@60 rpm). Theslurry was again mixed until homogenous and the final pH and % solidswere recorded. The metalized slurry was then used to coat theappropriate substrate.

A schematic representation of the process is presented as FIG. 15.

Example 3 Evaluation of the Effect of Doped ZrO-Based MMOSOs on NOLight-Off Temperature

The performance of the TWC catalyst systems containing Ln-ZrO₂-basedMMOSOs was evaluated by testing the catalysts on a synthetic gas flowreactor that closely simulates the engine-out gas chemistry andconditions (e.g., temperature) found in vehicles.

The catalyst systems containing 0.25% Rh (by weight) at a coating ofoxide at 125 g/L were tested (see Table 1) on a washcoat comprising anOSM made by either the IWCP or HTP process. A representative procedurefor making an OSM by the IWCP process is described in Example 10. Arepresentative procedure for making an OSM by the HTP process isdescribed in Example 11.

TABLE 1 Catalyst System (oxide used) Process NO_(x) T50 (° C.) a) 10%La—Al₂O₃ HTP 284.8 b) Nd_(0.05)Pr_(0.05)Ce_(0.30)Zr_(0.60)O₂ HTP 301.8IWCP 292.4 c) La_(0.10)Zr_(0.90)O₂ HTP 273.8 d) Pr_(0.10)Zr_(0.90)O₂ HTP274.7 IWCP 262.2

The catalyst formulations were aged by exposure to slightly rich exhaustfor 20 hours at 1000° C. and a space velocity of 12,000 hr⁻¹.Temperature: 1000° C.; Duration: 20 hours. The effects of theLn-ZrO₂-based MMOSOs on Rh catalytic performance in the TWC process werethen evaluated. Table 1 demonstrates the effect that variedLn-ZrO₂-based MMOSOs had on light-off temperatures after aging.

As can be seen from Table 1, Ln-doped ZrO₂ support oxides showed asignificant decrease in light-off temperature compared to thetraditional alumina-based support oxide.

Example 4 Evaluation of the Effect on NO_(x) and Hydrocarbon Conversionof Ln-ZrO₂-Based MMOSOs

The performance of TWC catalysts containing Ln-ZrO₂-based MMOSOs wasalso evaluated through vehicle testing.

Catalyst coatings were synthesized on conventional cordierite substratesand assembled into a system using a close-coupled catalyst (CC) and anunderfloor (UF) catalyst. Each catalyst system had a one-liter volumecapacity. The substrate contained 400 cells/in² and a wall thickness of3.5 mm

Each test system utilized the same washcoat containing Pd (concentration100 g/ft³ for both the CC and UF catalyst) and La—Al₂O₃ as a supportoxide.

In addition, each test system utilized Rh in the overcoat (concentration20 g/ft³ for the CC catalyst and 8.3 g/ft³ for the UF catalyst).However, the support oxide of the overcoat was varied to enable a directcomparison of the effects of the support oxide on Rh function in thecatalyst systems. Testing focused on performance after acceleratedengine aging cycles that have been established to simulate in-usevehicle aging approximating 150,000 miles of driving. The aging cyclecomprised exposing the catalyst systems to 950° C. for 200 hrs. Twodifferent controlled drive cycles were used to measure the tailpipeemissions: a) the Federal Test Procedure (see Table 2); and b) thehigh-speed cycle known as the US06 (see Table 3).

TABLE 2 Federal Test Procedure TWC Vehicle Performance With ThreeOvercoat Compositions. Federal Test Procedure Tailpipe EmissionsNon-Methane Overcoat Composition NO_(x) (g/mile) HC (g/mile) Standard40% OSM/60% La—Al₂O₃ 0.010 0.0067 Doping 40% OSM/30% La—Al₂O₃/ 0.00850.0065 30% Pr_(0.10)Zr_(0.90)O₂ 40% OSM/ 0.0088 0.0066 60%Pr_(0.10)Zr_(0.90)O₂

TABLE 3 US06 TWC vehicle Performance With Three Overcoat CompositionsUS06 Tailpipe Emissions Non-Methane Overcoat Composition NO_(x) (g/mile)HC (g/mile) Standard 40% OSM/60% Al₂O₃ 0.018 0.042 Doping 40% OSM/30%Al₂O₃/ 0.019 0.038 30% Pr_(0.10)Zr_(0.90)O₂ 40% OSM/ 0.011 0.034 60%Pr_(0.10)Zr_(0.90)O₂

The data from Table 2 shows the significant reduction in NO_(x)emissions with catalyst systems comprising Pr_(0.10)Zr_(0.90)O₂ supportoxides. Table 3 shows that the decrease of NO_(x) emissions is even moresignificant in the case of the high-speed, high-temperature US06 cyclefor the full substitution case. Table 3 also shows a significantreduction in hydrocarbon emissions with catalyst systems comprisingPr_(0.10)Zr_(0.90)O₂ support oxides.

Example 5 Evaluation of the Effect on Rh State of Ln-ZrO₂-Based MMOSOsUsing X-Ray Photoelectron Spectroscopy

As discussed herein, the ability of the Rh catalyst to participate inthe catalytic cycle depends on the state of Rh—i.e., Rh(0) vs Rh(III) asRh₂O₃ vs Rh(III)-MMO. X-ray Photoelectron Spectroscopy (XPS) was used toassess the relative proportion of these three Rh states in fresh(as-made) and aged TWC catalyst systems comprising differentLn-ZrO₂-based MMOSOs. The XPS technique measures changes in bindingenergy of the Rh 3d electrons. Changes in oxidation state of Rh have asignificant effect on binding energy—thus, shifts in binding energy canbe assigned to changes in Rh oxidation state. The chemical environmentof the Rh can also have a major impact on binding energy. For example, ahigher binding energy is indicative of a Rh interaction with the supportoxide—i.e., it is an indication that Rh(0) has interacted with thesupport oxide so as to form either Rh(III) as Rh₂O₃ or Rh(III)-MMO.

Detailed XPS scans were conducted on a Kratos Axis Ultra XPS system withan Al(mono) X-Ray source with the following characteristics: @270 W;Pass energy=20 eV; Step: 0.05 eV; Dwell time: 0.3 Second; Sweep: 5times; Binding energy: 318-298 eV; Charge neutralizer: On.

Supported Rh systems were calibrated using the corresponding support andcarbon tape (e.g. Zr 2p, O is and C 1s). A Rh metal film was used as areference to verify the calibration (Rh Foil (0.25 mm thickness, 99.9%,Aldrich) and a Rh₂O₃ oxide was used on the XPS system for the oxidereference (Rh₂O₃; Powder, 99.8%, Aldrich).

The standard catalyst system tested was 5% Rh (by weight) on 10%La—Al₂O₃. The Rh levels present in the standard catalysts were comparedto catalyst systems comprising 5% Rh (by weight) onPr_(0.10)Zr_(0.90)O₂MMOSOs.

The test samples were evaluated as follows:

-   -   1. After a 2% H₂ treatment for 1 hour at 150° C., all samples        were cooled to room temperature in the 2% H₂ gas flow. The        samples where then immediately transferred into a glove bag with        10% H₂—Ar.    -   2. In the glove bag filled with 10% H₂—Ar, the samples were        sealed in a gas-tight XPS sample holder.    -   3. The XPS sample holder was transferred into the preparation        chamber of the analyzer and held until the pressure was lower        than 1.0×10⁻⁶ torr before transfer to the XPS chamber for        measurement.

TABLE 4 XPS Data Showing Relative Proportions of Rh Forms Present (Basedon Oxidation States) in La—Al₂O₃ and Pr—ZrO₂ MMOSO Compositions %Rh(III) (Rh-M-Ox % Rh(III) mixed Catalyst system % Rh(0) (Rh₂O₃) oxide)Standard Fresh Rh/La—Al₂O₃ 52 43 5 Aged Rh/La—Al₂O₃ 42 7 42 Doping FreshRh/Pr_(0.10)Zr_(0.90)O₂ 78 22 0 MMOSO Aged Rh/Pr_(0.10)Zr_(0.90)O₂ 68 320 MMOSO

The relative proportions of Rh forms present in the catalyst systemswere measured: a) after freshly preparing the catalysts; and b) after 20hours of aging at 900° C. The data from Table 4 demonstrates severalbenefits of Rh/Pr—ZrO₂-based MMOSO catalysts when compared to theirRh/La—Al₂O₃ counterparts. First, TWC catalyst systems comprisingRh/Pr—ZrO₂-based MMOSOs contain higher amounts of Rh(0) when compared toTWC catalyst systems comprising La—Al₂O₃. Specifically, when compared tocatalysts containing Rh/La—Al₂O₃, Rh/Pr—ZrO₂-based MMOSO catalystscontain higher amounts of Rh(0) when they are initially formed, andthese catalysts are better able to maintain Rh(0) during the agingprocess. In addition, when TWC catalyst systems comprisingRh/Pr—ZrO₂-based MMOSOs are aged, they are able to retain essentiallyall the Rh as either Rh(0) or Rh(III) as reversible Rh₂O₃.Interestingly, not only is the vast majority of Rh present in theRh/Pr—ZrO₂-based MMOSO compositions maintained as Rh(0) (Rh(0):Rh(III)as Rh₂O₃=68:32), but the relative population of Rh(0):Rh(III) as Rh₂O₃is only moderately impacted by the aging process. However, whencatalysts comprising Rh/La—Al₂O₃ are exposed to the same aging process,both the Rh(0) and Rh(III) as reversible Rh₂O₃ initially present in thecomposition are converted to the inactive and irreversibly oxidizedRh(III)-MMO state in significant quantities. Note that none of theinactive and irreversible Rh(III)-MMO state was observed in either thefresh or aged Rh/Pr—ZrO₂-based MMOSO catalysts.

Example 6 Evaluation of the Effect on Catalyst Efficiency of Pr Dopingof ZrO₂-Based MMOSOs

The effect of the amount of Pr doping of the ZrO₂-based MMOSO oncatalyst efficiency was evaluated. In each of these experiments, thesame catalyst was used (single layer of 13 g/ft³ Rh) while the Prcontent of the Pr—ZrO₂-based MMOSO was varied. Specifically, the effectof Pr doping on the T90 temperature was evaluated. The T90 temperatureis the temperature at which the catalyst is capable of converting 90% ofthe passing exhaust compound (e.g., NO_(x) or hydrocarbon) after thecatalyst has been aged at 1000° C. for 10 hours.

TABLE 5 Efficiency of Catalyst systems Comprising Pr—ZrO₂-based MMOSOsCatalyst system NO T90 HC T90 Standard Support oxide: 40% OSM/ 375.0401.5 60% Al₂O₃ 40% OSM/60% X = 0.05 367.2 387.8 Pr_(x)Zr_(1−x)O₂ X =0.10 360.1 385.1 X = 0.15 357.1 388.1

The data from Table 5 show that catalyst systems comprisingPr—ZrO₂-based MMOSO exhibit lower light-off temperatures with respect toNO and hydrocarbon conversion. Thus, catalyst systems comprisingPr—ZrO₂-based MMOSOs are able to operate efficiently at lowertemperatures when compared to the relative to a reference aluminacatalyst.

Example 7 Evaluation of Amount of Reducible Rh in Ln-ZrO₂-Based MMOSOsUsing Hydrogen Temperature-Programmed Reduction and HydrogenChemisorption

Hydrogen Temperature-Programmed Reduction (H₂-TRP) and HydrogenChemisorption were used to evaluate the amount of reducible Rh (i.e.,R(0) or Rh(III) as Rh₂O₃) present in Ln-ZrO₂-based MMOSOs.

Samples were tested as follows using an AutoChem II 2920.

H₂-TPR Portion of Testing

-   -   1) Samples were exposed to a carrier gas (i.e., an atmosphere)        of 20% O₂—Ar. The temperature was raised at a rate of 20° C./min        to a final temperature of 300° C. The temperature was maintained        at 300° C. for 1 hour.    -   2) Samples were cooled to 40° C. in 20% O₂—Ar.    -   3) The carrier gas was changed to 100% Ar and the sample was        maintained until the thermal conductivity detector (TCD) signal        stabilized.    -   4) The samples were cooled to −50° C. in Ar. The temperature was        maintained for 5 minutes.    -   5) The carrier gas was change to 10% H₂—Ar and maintained at        −50° C. for 15 minutes.    -   6) TPR was carried out in 10% H₂—Ar, wherein the temperature was        increased from −50° C. to 550° C. at a rate of 20° C./min. The        temperature was then maintained at 550° C. for 30 minutes.

H₂-chemisorption Portion of Testing

-   -   7) Post TPR, the carrier gas was changed to Ar and the        temperature was maintained at 550° C. for 30 minutes.    -   8) The temperature was then reduced to 40° C. (with Ar as the        carrier gas).    -   9) The temperature was further cooled to −70° C. in Ar and        maintained until the TCD signal stabilized.    -   10) Chemisorption was carried out wherein 10% H₂—Ar Pulses were        administered until saturation at −70° C. in Ar was observed.

The TPO protocol consisted of exposing the catalyst to oxygen at thestated temperature. The XHFC protocol consisted of high-temperatureaging at the stated temperature in a fuel-cut gas chemistry (56 secondsstoichiometric, 4 s A/F=20) at a space velocity of 100,000 hr⁻¹.

The results of the testing are listed in Table 6.

TABLE 6 Rh Properties After H₂-chemisorption Reducible Rh Avg. RhSurface Area Rh Dispersion Particle Size* Sample Type of Testing (m²/gRh) (H/Rh, %) (nm) 0.6% Rh/ZrO₂ 550° C. TPO 182 41.3% 2.66 900° C. TPO104 23.7% 4.64 1000° C. XHFC 1.20 0.27% 403 (20 hours) 0.6% Rh/ 550° C.TPO 204 46.4% 2.37 Pr_(0.5)Zr_(0.95)O₂ MMOSO 900° C. TPO 122 27.7% 3.961000° C. XHFC 6.98 1.59% 69.3 (20 hours) 0.6% Rh/ 550° C. TPO 242 55.0%2.00 Pr_(0.10)Zr_(0.90)O₂ MMOSO 900° C. TPO 130 29.4% 3.73 1000° C. XHFC12.6 2.87% 38.3 (20 hours) 0.6% Rh/ 550° C. TPO 236 53.5% 2.05Pr_(0.15)Zr_(0.85)O₂ MMOSO 900° C. TPO 110 25.1% 4.38 1000° C. XHFC 13.02.95% 37.3 (20 hours) *Calculated based on complete Rh reduction

The results of the above testing are illustrated in FIGS. 10-14. As canbe seen by the data in those Figures, on the whole, catalyst systemscomprising Pr_(0.10)Zr_(0.90)O₂ MMOSO (10% Pr) as an Rh supportexhibited the highest total H₂ absorption capacity. This suggests thatsuch systems exhibit good oxygen storage capacity and good surface-redoxactive properties. In addition, increasing the Pr-content increasedstability against Rh sintering. Moreover, the Pr_(0.10)Zr_(0.90)O₂ MMOSO(10% Pr) samples contained nearly twice the amount of H₂ accessible Rhsurface after XHFC aging compared to the Pr_(0.10)Zr_(0.90)O₂ MMOSO (5%Pr) samples.

Example 8 Effect of Pr do s in of ZrO₂-Based MMOSOs on CatalystStructure

The effect of the amount of Pr doping of the ZrO₂-based MMOSO on theoverall structure of the washcoats or overcoats in which they arelocated was also tested. X-ray diffraction (XRD) was used to determinethe amount of tetragonal vs monoclinic phase present in catalyst systemscomprising various amounts of Pr doped onto ZrO₂-based MMOSO. Theresults are displayed in FIGS. 5 and 6.

XRD data was recorded on a Rigaku Mini Flex with accelerating voltage=30kV; electron beam current=15 mA; dwell time=1.2 seconds; scanincrement=0.02° 2Θ; with diffractometer optics: nickel filter ondetector; K_(α2) striping; and a scan range=10−70° 2Θ.

Increasing the amount of Pr doping above 5% lead to an increase in thestability of the tetragonal phase. This phenomenon is beneficial becausethe tetragonal phase of ZrO₂ is arranged in a manner which permitsfaster and easier diffusion of oxygen (i.e., oxygen motility) throughthe catalyst structure enhancing the activity of the catalyst. Inaddition, Pr present in the Ln-ZrO₂-based MMOSO is present as solidsolution and, thus, the MMOSO is composed of a single homogenous phase.This also allows for faster and easier diffusion of oxygen through thecatalyst structure (see FIGS. 7 and 8).

When considering phase stability and H₂ absorption capacity, 10% Prdoping yields optimal catalyst properties. As discussed above,increasing doping above 10% means that a large amount of larger Pr³⁺cations (when compared to the Zr⁴⁺ cations) are present in the catalystsystem. The Pr³⁺ cations may act as steric barriers to oxygen diffusionas the amount of Pr increases. This phenomenon is illustrated in FIG. 7.

Example 9 Effect of Pr Doping of ZrO₂-Based MMOSOs on Oxygen StorageCapacity

The effect of the amount of Pr doping of the ZrO₂-based MMOSO on theoxygen storage capacity (OSC) of washcoats containing Pr—ZrO₂-basedMMOSOs was evaluated. OSC is typically measured by exposing a sample toeither lean or rich air/fuel mixtures. In such environments, the samplemust either absorb O₂ from the exhaust stream (e.g., in lean air/fuelmixture environments) or release O₂ (e.g., in rich air/fuel mixtureenvironments) in order to maintain efficient catalysis of exhaustcompounds. The amount of time for which a sample can buffer thelean/rich air/fuel mixture is one way to quantify the OSC of a sample.This time is usually referred to as the “delay time”—i.e., the amount oftime that it takes for a perturbation in the air/fuel mixture tomanifest itself as a change in O₂ levels within the catalystenvironment. The delay time can also be measured by the amount of timethat it takes for a perturbation in the air/fuel mixture to manifestitself as a change in CO levels within the catalyst environment. Thus,the longer the delay time, the better the OSC of a sample.

As can be seen by the data in Table 7, increasing the amount of Prpresent in the MMOSOs has a positive effect on the OSC of the washcoat.The washcoat comprised: 120 g/L, 9.6M Ba Impregnation (12 g/ft³ Pd);OSM:support oxide (1:1.5) (12.7 g/ft³ Rh).

TABLE 7 OSC of Pr—ZrO₂-based MMOSOs O₂ delay time at CO delay time atSupport Oxide in Washcoat 575° C. (seconds) 575° C. (seconds) ZrO₂ 16.529.98  5% Pr—ZrO₂ 15.52 7.92 10% Pr—ZrO₂ 20.02 12.17 15% Pr—ZrO₂ 20.2913.47

Example 10 Generation of OSM Using the Improved Wet Chemical Process(IWCP)

In a representative IWCP procedure, Pd(NO₃)₂ was added to an aqueousslurry of milled OSM (30% CeO₂, 60% ZrO₂, 5% Nd₂O₃ and 5% Pr₆O₁₁).Tetraethylammonium hydroxide was then added to generate the IWCP-OSMslurry.

Separately, La—Al₂O₃ was milled with acetic acid at a pH of ˜6.0. BaCO₃was then added to the milled La—Al₂O₃ and stirred for approximately 5minutes. The La—Al₂O₃/BaCO₃ mixture was then added to IWCP-OSM slurryand the resulting composition was coated on to the washcoat which wascalcined to generate the Pd-OSM IWCP containing catalyst composition(see, FIG. 16).

Example 11 Generation of OSM Using the High Temperature Process (HTP)

Oxygen storage materials generated using the High Temperature Process(HTP) contain a metal catalyst (e.g., Pd) in a solid solution with theOSM (in this case a Ce-containing mixed metal oxide). Thus, OSMsgenerated using the HTP contain a metal catalyst which is evenlydispersed throughout the OSM and the surface of the OSM.

The HTP entails first mixing a Pd chemical precursor and an oxide OSM,and then spraying the mixture into a hot furnace. Typically, thetemperature of the furnace is between 300° C. and 500° C. and thetemperature of the hot zone of the furnace is greater than 500° C. In arepresentative experiment, the HTP OSM was generated by 1) co-milling(30% CeO₂, 60% ZrO₂, 5% Nd₂O₃ and 5% Pr₆O₁₁) and a Pd(NO₃)₂; and 2)spraying the resulting mixture of into a furnace.

1. A support oxide comprising ZrO₂ doped with an amount of lanthanide.2. The support oxide of claim 1, wherein said support oxide furthercomprises Al₂O₃ or La—Al₂O₃.
 3. The support oxide of claim 1, whereinsaid lanthanide is La or Pr.
 4. The support oxide of claim 1, whereinthe ZrO₂ is doped with between about 1-30% of said lanthanide.
 5. Thesupport oxide of claim 4, wherein the ZrO₂ is doped with between about5-15% of said lanthanide.
 6. The support oxide of claim 1, wherein saidsupport oxide comprises La_(X %)Zr_((1-X) %)O₂ and/orPr_(X %)Zr_((1-X) %)O₂.
 7. The support oxide of claim 6, wherein saidsupport oxide comprises La_(5%)Zr_(95%)O₂, Pr_(5%)Zr_(95%)O₂,La_(10%)Zr_(90%)O₂, Pr_(10%)Zr_(90%)O₂, La_(15%)Zr_(85%)O₂,Pr_(15%)Zr_(85%)O₂, or mixtures thereof.
 8. The support oxide of claim1, wherein said support oxide is in the tetragonal phase.
 9. The supportoxide of claim 1, wherein said support oxide further comprises an oxygenstorage material (OSM).
 10. A washcoat or overcoat comprising a supportoxide, an oxygen storage material (OSM) and a catalyst, wherein saidsupport oxide is according to claim
 1. 11. The washcoat or overcoat ofclaim 10, wherein said catalyst is a platinum group metal (PGM)catalyst.
 12. The washcoat or overcoat of claim 11, wherein said PGM isRh, Pt, Pd, or a mixture thereof.
 13. The washcoat or overcoat of claim12, wherein said PGM is Rh.
 14. The washcoat or overcoat of claim 13,wherein said Rh is present at 0.25% (by weight) of said washcoat. 15.The washcoat or overcoat of claim 10, wherein said support oxideconstitutes 1-100% (by weight) of said washcoat or overcoat.
 16. Awashcoat or overcoat comprising: a) (i) 40% oxygen storage material(OSM); (ii) 30% Al₂O₃ or La—Al₂O₃; and (iii) 30% Pr_(0.05)Zr_(0.95)O₂;b) (i) 40% OSM; (ii) 30% Al₂O₃ or La—Al₂O₃; and (iii) 30%La_(0.05)Zr_(0.95)O₂; c) (i) 40% OSM; 30% Al₂O₃ or La—Al₂O₃; and (iii)30% Pr_(0.10)Zr_(0.90)O₂; d) (i) 40% OSM; 30% Al₂O₃ or La—Al₂O₃; and(iii) 30% La_(0.10)Zr_(0.90)O₂; e) (i) 40% OSM; 30% Al₂O₃ or La—Al₂O₃;and (iii) 30% Pr_(0.15)Zr_(0.85)O₂; f) (i) 40% OSM; 30% Al₂O₃ orLa—Al₂O₃; and (iii) 30% La_(0.15)Zr_(0.85)O₂; g) (i) 40% OSM; and (ii)60% Pr_(0.05)Zr_(0.95)O₂; h) (i) 40% OSM; and (ii) 60%La_(0.05)Zr_(0.95)O₂; i) (i) 40% OSM; and (ii) 60% Pr_(0.10)Zr_(0.90)O₂;j) (i) 40% OSM; and (ii) 60% La_(0.10)Zr_(0.90)O₂; k) (i) 40% OSM; and(ii) 60% Pr_(0.15)Zr_(0.85)O₂; or l) (i) 40% OSM; and (ii) 60%La_(0.15)Zr_(0.85)O₂.
 17. A washcoat or overcoat according to claim 15,wherein said OSM is:Ce_(1-a-b-c-d)D_(a)E_(b)F_(c)Zr_(d)O₂, wherein: a, b and c are,independently, 0-0.7; d is 0-0.9; and D, E and F are, independently,selected from the group consisting of lanthanides, alkaline earth metalsand transition metals.
 18. A washcoat or overcoat according to claim 17,wherein said OSM is Ce_(0.3)Nd_(0.05)Pr_(0.05)Zr_(0.6)O₂.
 19. A catalystsystem comprising: a substrate and a washcoat, wherein said washcoat isaccording to claim
 10. 20. A catalyst system comprising: a substrate, awashcoat, and an overcoat, wherein said washcoat is according to claim10; and said overcoat comprises a support oxide, an oxygen storagematerial (OSM), and a catalyst.
 21. A catalyst system comprising: asubstrate, a washcoat, and an overcoat, wherein said washcoat comprisesa support oxide, an oxygen storage material (OSM) and a catalyst; andwherein said overcoat is according to claim
 10. 22. The catalyst systemof claim 21, wherein said catalyst in said overcoat is a platinum groupmetal (PGM) catalyst.
 23. The catalyst system of claim 22, wherein saidcatalyst in said overcoat is Rh, Pt, Pd, or a mixture thereof.
 24. Thecatalyst system of claim 23, wherein said catalyst in said overcoat isPd.
 25. The catalyst system of claim 24, wherein said Pd is present at100 g/ft³.
 26. The catalyst system of claim 21, wherein said catalyst insaid washcoat is a platinum group metal (PGM) catalyst.
 27. The catalystsystem of claim 26, wherein said catalyst in said washcoat is Rh, Pt,Pd, or a mixture thereof.
 28. The catalyst system of claim 27, whereinsaid catalyst in said washcoat is Pd.
 29. The catalyst of claim 28,wherein said Pd is present at 100 g/ft³.
 30. The catalyst system ofclaim 19, wherein said catalyst system is a three way conversioncatalyst system.
 31. The catalyst system of claim 19, wherein saidcatalyst system exhibits improved gas flow when compared to catalystsystems comprising only traditional support oxides.
 32. The catalystsystem of claim 19, wherein said catalyst system exhibits improvedlight-off performance when compared to catalyst systems comprising onlytraditional support oxides.
 33. A method of making a catalyst systemcomprising: a) depositing a washcoat according to claim 10 on asubstrate; b) treating said washcoat and substrate by calcination; andc) optionally impregnating a platinum group metal (PGM) catalyst intosaid washcoat, followed by drying and calcination.
 34. A method ofmaking a catalyst system comprising: a) depositing a washcoat accordingto claim 10 on a substrate; b) treating said washcoat and substrate bycalcination; c) optionally impregnating a platinum group metal (PGM)catalyst into said washcoat, followed by drying and calcination; d)depositing an overcoat onto the washcoat; wherein said overcoatcomprises a support oxide, an oxygen storage material and a catalyst; e)optionally impregnating a PGM catalyst into said overcoat, followed bydrying and calcination.
 35. A method of making a catalyst systemcomprising: a) depositing a washcoat on a substrate, wherein saidwashcoat comprises a support oxide, an oxygen storage material and acatalyst; b) treating said washcoat and substrate by calcination; c)optionally impregnating a platinum group metal (PGM) catalyst into saidwashcoat, followed by drying and calcination; d) depositing an overcoataccording to claim 10 onto the washcoat; e) optionally impregnating aPGM catalyst into said overcoat, followed by drying and calcination. 36.(canceled)
 37. (canceled)
 38. (canceled)
 39. (canceled)
 40. (canceled)